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NADP Scientific Symposium Agenda

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NADP Annual Meeting and Scientific Symposium

San Diego, California

October 30–November 3, 2017

Monday, October 30, 2017 Room Location

9:00 a.m. – 12:00 p.m. CLAD Shell

10:00 a.m. – 12:00 p.m. AMSC Del Mar

12:30 p.m. – 4:30 p.m. TDEP Del Mar

3:00 p.m. – 5:00 p.m. CLAD Shell

Tuesday, October 31, 2017

Open All Day Registration Desk Mezzanine

8:30 a.m. – 10:00 a.m. Joint Subcommittee Meeting Bay E

10:00 a.m. – 10:15 a.m. Break Foyer

10:15 a.m. – 12:00 p.m. Subcommittee Meetings

Network Operations Bay E

Ecological Response and Outreach Del Mar

Critical Loads Shell

12:00 p.m. – 1:30 p.m. Lunch on your own

1:30 p.m. – 2:30 p.m. Joint Subcommittee Meeting Bay E

2:30 p.m. – 3:00 p.m. Break Foyer

3:00 p.m. – 6:00 p.m. Executive Committee Meeting Del Mar

6:00 p.m. City Dep Ad-hoc Subcommittee Shell

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Wednesday, November 1, 2017 Room Location

Open All Day Registration/Office Mission Foyer

8:00 a.m. – 8:30 a.m. Welcome, Program Office Report Mission A, B, C, D

Awards and Announcements

Tamara Blett: NADP Vice Chair, Symposium Chair

National Park Service

Donna Schwede: NADP Chair

U.S. EPA

8:30 a.m. – 9:15 a.m. Mapping the Future of NADP

NADP Executive Committee

9:15 a.m. – 10:00 a.m. Annual State of the NADP Report

David Gay: NADP Program Coordinator

10:00 a.m. – 10:30 a.m. Break Mission Foyer

Technical Session 1: Critical Loads: Acidification and Excess Nitrogen Thresholds

Session Chair: Mike Bell

National Park Service

10:30 a.m. – 10:50 a.m. Developing Critical Loads of Acidity for Stream

Ecosystems in the Adirondack Region of New York State Shuai Shao, Syracuse University

10:50 a.m. – 11:10 a.m. Critical Load of Sulphur and Nitrogen for Terrestrial

Ecosystems in Alberta, Canada: Sensitivity to Input Data Yayne-abeba Aklilu, Government of Alberta

11:10 a.m. – 11:30 a.m. Extreme nitrogen saturation of serpentine grasslands in Santa

Clara County, California: A nexus for conservation action Stuart Weiss, Creekside Center for Earth Observation

11:30 a.m. – 11:50 a.m. Individual tree species’ responses to concurrent nitrogen and

sulfur deposition across the contiguous United States Kevin Horn, Forest Resources and Environmental Conservation,

Virginia Tech

11:50 a.m. – 12:10 p.m. Critical loads of nitrogen deposition for trees and forest

ecosystems across the continental U.S.

Linda Pardo, USDA Forest Service

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Wednesday, November 1, 2017 Room Location

Mission A, B, C, D

12:10 p.m. – 12:30 p.m. Recent Advances in Critical Loads Research

Christopher Clark, US EPA

12:30 p.m. – 2:00 p.m. Lunch on your own

Technical Session 2: Air & Water Quality: Linkages and Synergies

Session Chairs: Mark Nilles and Helen Amos

USGS and US EPA

Moderator: Rich Pouyat, USDA Forest Service

2:00 p.m. – 2:20 p.m. Bridging the air-water quality information gap to improve

nutrient management Helen Amos, AAAS Fellow hosted by US EPA

2:20 p.m. – 2:40 p.m. CMAQ modeling in the nitrogen inventory study in the

Nooksack-Abbotsford-Sumas Transboundary Region Donna Schwede, US EPA

2:40 p.m. – 3:00 p.m. Episodic Acidification in the Adirondack Region of New York:

Spatial Patterns and Evidence of Recovery

Douglas Burns, U.S. Geological Survey

3:00 p.m. – 3:30 p.m. Break

Technical Session 3: Air & Water Quality: Linkages and Synergies (cont.) Session Chairs: Mark Nilles and Helen Amos

USGS and US EPA

Moderator: Rich Pouyat, USDA Forest Service

3:30 p.m. – 3:50 p.m. Changes in stream chemistry at high flow during 23 years of

decreasing acid deposition in the Catskill Mountains of New

York Michael McHale, U.S. Geological Survey

3:50 p.m. – 4:10 p.m. Evaluating Potential Water Quality Impairments on National

Forest Priority Watersheds Using Estimates of Atmospheric

Deposition

David Levinson, U.S. Forest Service

4:10 p.m. – 4:30 p.m. Integration of atmospheric deposition and water

quality monitoring in the El Yunque National Forest, Puerto

Rico

Anita K. Rose, USDA Forest Service

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Wednesday, November 1, 2017 Room Location

4:30 p.m. – 5:30 p.m. Break

5:30 p.m. – 8:00 p.m. Poster Session and Reception William D. Evans

Thursday, November 2, 2017 Room Location

Open All Day Registration/Office Mission Foyer

Thursday, November 2, 2017 Room Location

Mission A, B, C, D

8:00 a.m. – 8:10 a.m. Opening Remarks, Announcements, and Overview of Day 2

Tamara Blett, NADP Vice Chair,

National Park Service

8:10 a.m. – 8:40 a.m. Keynote Address

Dr. Lynn Russell

Professor of Atmospheric Chemistry

Scripps Institution of Oceanography

Technical Session 4: Deposition Modeling and Monitoring

Session Chair: Anne Rea and Eric Prestbo

USDA Forest Service and Tekran

8:40 a.m. – 9:00 a.m. Evaluation of wet atmospheric deposition along the coast of

the Gulf of Mexico:- An international collaboration

opportunity

Rodolfo Sosa, Universidad Nacional Autonoma de Mexico

9:00 a.m. – 9:20 a.m. Methylmercury and total mercury in marine stratus cloud and

fog water: Sources, sinks, and lifetimes Peter Weiss-Penzias, University of California, Santa Cruz,

9:20 a.m. – 9:40 a.m. Trends in NADP bromide wet deposition concentrations,

2001-2016

Gregory Wetherbee, U.S. Geological Survey

9:40 a.m. – 10:00 a.m. Total deposition by measurement-model fusion using ADAGIO

Amanda Cole, Environment and Climate Change Canada

10:00 a.m. – 10:30 a.m. Break

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Thursday, November 2, 2017 Room Location

Mission A, B, C, D

Technical Session 5: Urban Air Quality and Deposition

Session Chair: Steven Decina

Boston University

10:30 a.m. – 10:50 a.m. Quantifying urban nitrogen emission and deposition through

optical sensing techniques Kang Sun, Harvard-Smithsonian Center for Astrophysics

10:50 a.m. – 11:10 a.m. Using Moss to Detect Fine-Scaled Deposition of Heavy Metals

in Urban Environments

Sarah Jovan, U.S. Forest Service Pacific Northwest Research

Station

11:10 a.m. – 11:30 a.m. Elemental carbon deposition to urban tree canopies:

Magnitudes and spatial patterns

Alexandra G. Ponette-González, Department of Geography and

The Environment, University of North Texas

11:30 a.m. – 11:50 a.m. Characteristics and Ecological Impacts of Atmospheric

Deposition in Urban and Urban-Affected Regions

Mark Fenn, USDA Forest Service, PSW Research Station

11:50 a.m. – 12:10 p.m. Assessing Sources and Fluxes of Reactive Nitrogen Deposition

to Urban Landscapes Using Ion Exchange Resins

Rebecca Forgrave, University of Pittsburgh

12:10 p.m. – 12:30 p.m. Increasing ethanol consumption as a renewable fuel: How will

vehicle ethanol emissions impact the urban atmosphere? J. David Felix, Texas A&M University - Corpus Christi

12:30 p.m. – 2:00 p.m. Lunch on your own

Technical Session 6: Nitrogen: Transport Deposition and Effects

Session Chair: Justin Valliere

University of California Los Angeles

2:00 p.m. – 2:20 p.m. Ecosystem flip-flops in response to anthropogenic N

deposition: The importance of long-term experiments

George Vourlitis, California State University

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Thursday, November 2, 2017 Room Location

Mission A, B, C, D

2:20 p.m. – 2:40 p.m. Organic nitrogen in aerosols at a forest site in southern

Appalachia John Walker, US EPA

2:40 p.m. – 3:00 p.m. Quantifying nitrogen deposition inputs and impacts on plant

richness in a Mediterranean-type shrubland

Justin Valliere, University of California Los Angeles

3:00 p.m. – 3:30 p.m. Break

Technical Session 7: Nitrogen: Transport Deposition and Effects (cont.)

Session Chair: Justin Valliere

University of California Los Angeles

3:30 p.m. – 3:50 p.m. Atmospheric deposition evaluation as a tool to preserve urban

natural green areas: Mexico City case

María Alejandra Fonseca

3:50 p.m. – 4:10 p.m. Spatial and temporal relationships of key nitrogen species

between ambient and deposition regimes

Richard Scheffe, US EPA

4:10 p.m. – 4:30 p.m. Nutrient deposition in the headwaters of streams may impact

nitrogen loading in Southern Californian estuaries Pamela Padgett, USDA Forest Service

4:30 p.m. – 4:50 p.m. Contributions of organic nitrogen to the gas phase and

speciation of amines in ambient samples Katherine Benedict, Colorado State University

Friday, November 3, 2017 Room Location

Open A.M. Session Registration/Office Mission Foyer

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Friday, November 3, 2017 Room Location

Mission A, B, C, D

8:00 a.m. – 8:10 a.m. Opening Remarks, Announcements, and Overview of Day 3

Tamara Blett, NADP Vice Chair

National Park Service

Technical Session 8: Ammonia Emissions, Trends, Deposition

Session Chair: Katie Benedict

Colorado State University

8:10 a.m. – 8:30 a.m. Investigation of hourly concentration ratios of ammonia gas

and particulate ammonium at CASTNet site in Beltsville, MD

Greg Beachley, US EPA

8:30 a.m. – 8:50 a.m. Urban and On-Road Emissions: Underappreciated Sources of

Atmospheric Ammonia

Mark Fenn, USDA Forest Service, PSW Research Station

8:50 a.m. – 9:10 a.m. “Fingerprinting” Vehicle-Derived Ammonia Utilizing

Nitrogen Stable Isotopes Wendell Walters, Brown University

9:10 a.m. Adjourn

8:30 a.m. – 6:00 p.m. Optional Field Trips – Marine ecosystem field trip by kayak to

LaJolla Sea Caves (morning trip 8:30 departure from hotel and

afternoon trip 12:30 p.m. departure from hotel)

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2017 NADP SITE OPERATOR AWARDS

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KEYNOTE SPEAKER DR. LYNN RUSSELL, PROFESSOR OF CLIMATE, ATMOSPHERIC SCIENCE AND PHYSICAL OCEANOGRAPHY – SCRIPPS INSTITUTE OF OCEANOGRAPHY, UC SAN DIEGO

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Biography

Professor of Atmospheric Chemistry

Lynn M. Russell is Professor of Atmospheric Chemistry at Scripps

Institution of Oceanography on the faculty of University of California at San

Diego, where she has led the Climate Sciences Curricular Group since

2009. Her research is in the area of aerosol particle chemistry, including the

behavior of particles from both biogenic and combustion processes. Her

research group pursues both modeling and measurement studies of

atmospheric aerosols, using the combination of these approaches to

advance our understanding of fundamental processes that affect

atmospheric aerosols. She completed her undergraduate work at Stanford

University, and she received her Ph.D. in Chemical Engineering from the

California Institute of Technology for her studies of marine aerosols. Her

postdoctoral work as part of the National Center for Atmospheric Research

Advanced Studies Program investigated aerosol and trace gas flux and

entrainment in the marine boundary layer. She served on the faculty of

Princeton University in the Department of Chemical Engineering before

accepting her current position at Scripps in 2003. She has been honored

with young investigator awards from ONR, NASA, Dreyfus Foundation,

NSF, and the James S. McDonnell Foundation, and she received the

Kenneth T. Whitby Award from AAAR (2003) for her contributions on

atmospheric aerosol processes and the Princeton Rheinstein Award for

excellence in teaching and scholarship (1998).

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TECHNICAL SESSION 1:

CRITICAL LOADS: ACIDIFICATION AND

EXCESS NITROGEN THRESHOLDS

Session Chair: Mike Bell,

National Park Service

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Developing Critical Loads of Acidity for Stream Ecosystems in the

Adirondack Region of New York State

Shuai Shao1, Charles T. Driscoll

2, Douglas A. Burns

3, Gregory B. Lawrence

4 and

Timothy J. Sullivan5

The Adirondack region of New York has high inputs of acidic deposition and many acidic

streams. The PnET-BGC is an integrated biogeochemical model formulated to simulate the

response of soil and surface waters in northern forest ecosystems to changes in atmospheric

deposition. In this is study, the model was applied to twenty-one streams in the Adirondacks to

simulate the effects of past and future (1000-2200) changes in atmospheric sulfur (S) and

nitrogen (N) deposition on stream water chemistry. The model was calibrated using observed

stream water and soil chemistry data. The results indicated model simulated stream water

chemistry generally agreed with the measured data at all sites. Model hindcasts indicated that

stream water in the Adirondack are inherently sensitive to acidic deposition. The average of

model simulated stream ANC is 175 μeq/L (range 48 to 335 μeq/L) before anthropogenic

disturbances are applied to the model (1850) and it decreased in response to historical acidic

deposition to 59 μeq/L (−37 to 242 μeq/L) in 2015. The model was run under a range of future

scenarios from 2016 to 2200 of changes in sulfate, nitrate, and combination of sulfate and nitrate

deposition to evaluate how the stream water chemistry might respond to emission control

strategies. Future model projections suggested that decreases in sulfate deposition is more

effective in increases in stream ANC compared with equivalent decreases in nitrate deposition;

nevertheless, the simultaneous controls on nitrate and sulfate deposition are more effective way

to restore stream ANC than individual control of nitrate or sulfate deposition. However, only ten

of the twenty-one sites will restore the stream ANC to the preindustrial level under the most

aggressive deposition reduction scenarios. The model results were used to determine the critical

loads of acidity (CLs, the level of atmospheric deposition above which the harmful ecosystem effects occur) for all twenty-one sites.

1Syracuse University, sshao@syr.edu 2Syracuse University, ctdrisco@syr.edu 3U.S. Geological Survey, daburns@usgs.gov 4U.S. Geological Survey, glawrenc@usgs.gov 5E&S Environmental Chemistry, tim.sullivan@esenvironmental.com

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Critical Load of Sulphur and Nitrogen for Terrestrial Ecosystems in

Alberta, Canada: Sensitivity to Input Data

Yayne-abeba Aklilu1, Laura Blair

2, Gordon Dinwoodie

3, Julian

Aherne4, Naomi Tam

5 and Sunny Cho

6

The steady state mass balance model (SSMB) was used to calculate the critical loads of acidity:

the maximum critical loads for sulphur (CLmax(S)) and nitrogen (CLmax(N)) deposition and the

minimum critical load for nitrogen deposition (CLmin(N)). These critical loads were calculated for

terrestrial ecosystems in the province of Alberta. While SSMB is relatively simple to use, the

challenge in using this model lies in estimating the required input especially for large study area

such as a province (661,848 km2). Base cation weathering and appropriate application of

chemical criteria are two such critical inputs. For this work, the soil texture approximation

method and soils information from a national soil database was used to determine base cation

weathering. The chemical criteria, base cation to aluminum ratio, used to determine acid

neutralizing capacity leaching was applied by land use. Higher CLmax(S) and CLmax(N) (> 600 eq

ha-1yr-1) resulted for areas of the province with deeper soil and higher clay content providing the

conditions which can result in higher base cation weathering. CLmax(S) and CLmax(N) less than

200 eq ha-1yr-1 were determined for areas with sandy acidic soils as well as soils with higher

organic content. The distribution of CLmin(N) reflects biomass nitrogen content and removal of

harvested biomass. For the most part CLmin(N)was less than 100 eq ha-1yr-1 with some areas

having a CLmin(N) less than 50 eq ha -1yr-1. Areas with CLmin(N) greater than 50 eq ha-1yr-

1 contain managed forests which have notable nitrogen removal rates from biomass harvest and

removal. Exceedance of critical loads can indicate areas of potential ecosystem impact and areas

that need focused deposition monitoring. Exceedances and sensitivity of these exceedances are

explored using modelled sulphur and nitrogen deposition and calculated critical loads of acidity.

The findings are used to better inform the precipitation monitoring network for the province.

1Government of Alberta, yayne-abeba.aklilu@gov.ab.ca 2Government of Alberta, Laura.Blair@gov.ab.ca 3Government of Alberta, Gordon.Dinwoodie@gov.ab.ca 4University of Trent, jaherne@trentu.ca 5Government of Alberta, Naomi.tam@gov.ab.ca 6Government of Alberta, Sunhee.cho@gov.ab.ca

25

Extreme Nitrogen Saturation of Serpentine Grasslands in Santa Clara County,

California: A Nexus for Conservation Action

Stuart Weiss1 and Meredith Hastings

2

Serpentine grasslands are nutrient-poor, low biomass ecosystems that harbor high native

biodiversity including many listed species such as the Bay checkerspot butterfly. Research since

the 1990s has documented the threat of atmospheric nitrogen deposition from upwind Silicon

Valley that allows non-native annual grasses to overrun the dazzling displays of low-statured

wildflowers, and that the grass invasions are controlled by managed cattle grazing. The

estimated critical load for serpentine grasslands is 6 kg-N ha-1 year-1. Since 2015, in the high

deposition zone (10-20 kg-N ha-1 year-1 ), spring water nitrate up to 25 ppm (as NO3-) were

measured in baseflow, levels higher than any reported for non-agricultural sites in California.

Nitrate levels in samples from low deposition areas were 1-5 ppm. Isotopic analyses including

Δ17O show that 50-60% of the nitrate in spring and well water is unprocessed atmospheric

nitrate. Passive samplers, CMAQ models, N-cycling measurements, and emissions

inventories/projections are used to interpret the findings. High levels of nitric acid in summer

and low ecosystem capacity for N-retention in the fall growing season allow for flushing of

accumulated dry NO3 deposition into the fractured bedrock, and eventually into the springs.

Increased N-deposition from highway improvements and development was a major regulatory

nexus for the Santa Clara Valley Habitat Plan, a Habitat Conservation Plan/Natural Communities

Conservation Plan (HCP/NCCP). A novel nitrogen fee based on car trips generated is one of the

funding mechanisms, driving a need for cost-effective and robust monitoring of N-deposition

trends over the 50-year plan and beyond. A set of sentinel springs for long-term monitoring will

be identified and sampled on an interval commensurate with shallow groundwater residence

times.

1Creekside Center for Earth Observation, stu@creeksidescience.com 2Brown University, Meredith_Hastings@brown.edu

26

Individual Tree Species’ Responses to Concurrent Nitrogen and Sulfur Deposition

across the Contiguous United States

Kevin Horn1, R. Quinn Thomas

2, Linda H. Pardo

3, Christopher M. Clark

4, Mark

E. Fenn5, Gregory B. Lawrence

6, Steven S. Perakis

7, Erica A.H. Smithwick

8,

Douglas Baldwin9, Sabine Braun

10 and et al.

11

Atmospheric deposition of nitrogen (N) and sulfur (S) concurrently impact temperate forests through similar

and diverse mechanisms. Both N and S compounds contribute to soil acidification; however, N deposition also affects individual tree physiology and stand competition through eutrophication. Tree responses to S and

N deposition can be difficult to separate, especially since N and S deposition often originate from common sources. Additionally, tree responses to deposition are controlled by individual species physiologies and the

influence of local soil and climatic factors. Understanding the impacts of S and N deposition, both separate

and concerted, on demographics of tree species will help identify how forests and forest resources are changing, and facilitate setting response thresholds for N and S deposition.

Here we examine tree growth and survival rates against modeled N and S deposition and climate at the species level for the contiguous United States. Of the 94 species examined, growth and/or survival of 74 and

66 tree species were associated with S and/or N deposition, respectively. Only 5 species showed no

relationship with S or N deposition in either growth or survival. Of the 94 tree species, 30 tree species increased in growth with N deposition, 6 decreased, and 19 increased then decreased while 39 showed no

relationship with N deposition. For survival, 5 increased, 6 decreased, and 26 increased then decreased while

57 did not change across N deposition gradients. Only non-positive responses to S deposition were allowed in the models, for which 41 and 51 of the 94 species showed negative growth and survival responses,

respectively. When N deposition was considered without S deposition in the models, growth and survival

responses associated with N deposition decreased from an average rate of 17 Δkg C/Δkg N to 9.9 Δkg C/Δkg N and -0.065 Δ%P(s)/Δkg N ha-1yr-1 to -0.441 Δ%P(s)/Δkg N ha-1yr-1. Surprisingly, the presence of S

deposition in the models affected observed N deposition responses regardless of the correlation between N

and S inputs. Nonetheless, forest sensitivities to N and S deposition seemed to be associated with species-specific mechanisms as co-occurring species often demonstrated contrasting responses. These relationships of

tree species dynamics across highly variable N and S deposition gradients provide estimates for N and S

deposition impacts on forests in the U.S. and identify quantifiable thresholds for species responses to N and S deposition.

1Forest Resources and Environmental Conservation, Virginia Tech, Cheatham Hall, Blacksburg, VA 24061, kjhorn@vt.edu 2Forest Resources and Environmental Conservation, Virginia Tech, rqthomas@vt.edu 3USDA Forest Service, Northern Research Station, Burlington, VT 05405, lpardo@fs.fed.us 4US EPA, National Center for Environmental Assessment, Washington, DC 20460,

clark.christopher@epa.gov 5USDA Forest Service, Pacific Southwest Research Station, Riverside, CA 92507, mfenn@fs.fed.us 6U.S. Geological Survey, Troy, NY 12180, glawrenc@usgs.gov 7Forest and Rangeland Ecosystem Science Center, US Geological Survey, Corvallis, OR 97331,

sperakis@usgs.gov 8Department of Geography, The Pennsylvania State University, University Park, PA 16802,

smithwick@psu.edu 9Department of Geography, The Pennsylvania State University, University Park, PA 16802, dcb5006@gmail.com 10Umeå Plant Science Centre, Umea, Swedish University of Agricultural Sciences, Sweden,

sabine.braun@iap.ch 11Umeå Plant Science Centre, Umea, Swedish University of Agricultural Sciences, Sweden,

sabine.braun@iap.ch

27

Critical Loads of Nitrogen Deposition for Trees and Forest Ecosystems across the

Continental U.S.

Linda Pardo1, Kevin J. Horn

2, Christopher M. Clark

3 and R. Quinn Thomas

4

Critical loads of nitrogen deposition and exceedance of critical loads are being used increasingly

by resource managers and policy makers to assess the risk of detrimental effects to forests. A

recent analysis has allowed us to calculate critical loads for tree growth and survival in a

systematic way for over fifty species across the continental US.

We used United States Forest Service Forest Inventory and Analysis (FIA) data with modeled S

and N deposition rates and climate data to identify species-specific responses of trees associated

with S and N deposition across the conterminous United States. Growth and survival estimates

were made from repeated measurements of more than 1.1 million individual trees measured

between 2000 and 2016.

We used these data to set critical loads for growth (for 32 species) and survival (for 54 species)

for individual tree species and for level 3 ecoregions across the continental US. Using FIA

expansion factors we were able to assess the extent of forest area at risk from nitrogen deposition.

These species-specific responses will allow resource managers to understand the likely impacts

from atmospheric nitrogen deposition and to manager their forests accordingly. The critical loads

and exceedance maps will allow policy makers to assess the likely impacts of current and future

deposition scenarios.

1US Forest Service, lpardo@fs.fed.us 2Virginia Tech, kjhorn@vt.edu 3US EPA, Clark.Christopher@epa.gov 4Virginia Tech, rqthomas@vt.edu

28

Recent Advances in Critical Loads Research

Christopher Clark1, Kevin Horn

2, Linda Pardo

3, Robert Sabo

4, Jen Phelan

5, Jason

Lynch6 and Quinn Thomas

7

Nitrogen and sulfur deposition have declined in the eastern U.S. since the 1980s and 1990s

following the 1990 Amendments to the Clean Air Act, yet they remain significantly elevated

above thresholds where sensitive ecological end points are affected. Here we summarize several

projects on assessing ecosystem sensitivity to N and S deposition, and the ecosystem services

affected. One focus of the talk is on forest health and biodiversity, and here we use recently

available critical loads for 94 tree species to examine how individual tree species are affected

across the conterminous U.S. We also explore methods for synthesizing this information to

inform development of air quality policies under the secondary standards of the NAAQS. The

views expressed here are those of the authors and do not necessarily represent the views or

policies of the U.S. Environmental Protection Agency.

1US EPA, clark.christopher@epa.gov 2Virginia Polytechnical University 3US Forest Service 4US EPA 5University of Illinois 6US EPA 7Virginia Polytechnical University

29

TECHNICAL SESSION 2:

AIR & WATER QUALITY: LINKAGES AND

SYNERGIES

Session Chairs: Mark Nilles and Helen Amos,

USGS and US EPA

Session Moderator: Rich Pouyat, USDA Forest

Service

30

31

Bridging the Air-Water Quality Information Gap to Improve Nutrient

Management

Helen Amos1, Chelcy Miniat

2, Lori A. Sprague

3, David Gay

4, Mark A. Nilles

5,

Anne W. Rea6, Richard V. Pouyat

7, Denice M. Shaw

8, Jerad Bales

9, Jeff Deacon

10,

Jana E. Compton11

, Doug Burns12

, Jason A. Lynch13

, LaToya Myles14

, Pamela H.

Templer15

, John T. Walker16

and Dave Whitall17

Nutrient (nitrogen and phosphorus) enrichment in fresh and coastal waters is one of today’s most

pervasive, expensive, and challenging water quality issues in the US. Continued inputs of excess

nitrogen (N) and phosphorus (P) have created chronic drinking water contamination, harmful

algal blooms, and persistent hypoxic zones in some aquatic systems. Atmospheric deposition can

be a significant non-point source of N and P over large regions of the continental U.S. - yet there

is a shortage of coordinated information about how air quality impacts aquatic nutrient

enrichment. WADeIn (Water Quality & Atmospheric Deposition Integration) is an interagency,

multi-organization collaboration that aims to fill this gap and improve the coordination and

integration of atmospheric deposition and surface water quality monitoring to better understand

the sources, transport, and impacts of excess N and P. We present a call for better integration of

atmospheric deposition and water quality monitoring for N and P at a national scale that

leverages existing infrastructure and expertise with the long-term objective to develop an

integrated air/water monitoring consortium. We examine several issues driving the need for

enhanced integrated monitoring, including: coastal eutrophication, urban hotspots of deposition,

shift from oxidized to reduced N deposition, land-use change and land management, and

disappearance of pristine lakes. We offer specific next steps to move the U.S. towards a 21st-century integrated air/water monitoring consortium for improved management of ecosystems.

1AAAS Fellow hosted by US EPA, amos.helen@epa.gov 2US Department of Agriculture, Chelcy.Miniat@osec.usda.gov 3US Geological Survey, lsprague@usgs.gov 4University of Illinois, dgay@illinois.edu 5US Geological Survey, manilles@usgs.gov 6US Environmental Protection Agency, rea.anne@epa.gov 7US Forest Service, rpouyat@fs.fed.us 8US Environmental Protection Agency, shaw.denice@epa.gov 9Consortium of Universities for the Advancement of Hydrologic Science, Inc.,

jdbales@cuahsi.org 10US Geological Survey, jrdeacon@usgs.gov 11US Environmental Protection Agency, compton.jana@epa.gov 12US Geological Survey, daburns@usgs.gov 13US Environmental Protection Agency, lynch.jason@epa.gov 14NOAA, latoya.myles@noaa.gov 15Boston University, ptempler@bu.edu 16US Environmental Protection Agency, Walker.Johnt@epa.gov 17NOAA, dave.whitall@noaa.gov

32

CMAQ Modeling in the Nitrogen Inventory Study in the Nooksack-

Abbotsford-Sumas Transboundary Region

Donna Schwede

1, Ellen Cooter

2, Jiajia Lin

3, Jana Compton

4 and Jill Baron

5

Optimizing nitrogen (N) use for food production while minimizing the release of N and co-

pollutants to the environment is an important challenge. The Nooksack-Abbotsford-Sumas

Transboundary (NAS) Region, spanning a portion of the western interface of British Columbia,

Washington State, the Lummi Nation and Nooksack Tribal lands, supports agriculture, estuarine

fisheries, diverse wildlife, and vibrant urban areas. Excess N has contributed to surface and

ground water pollution, shellfish closure, and impaired air quality (such as haze or smog) in some

areas in the NAS Transboundary region. To reduce the release of N to the environment,

collaborative approaches that engage all stakeholders and appropriate institutions are needed to

integrate science, outreach and management efforts. The goal of the NAS Transboundary N

inventory study is to quantify the sources and fate of N, including inputs and transfers within the

watershed. We are synthesizing publicly available data on N sources including atmospheric

deposition, sewage and septic inputs, fertilizer and manure applications, marine-derived N from

salmon migrations, natural N-fixing vegetation, and more.

CMAQv5.2 is used to estimate daily total nitrogen deposition as well as other air quality

indicators in the target year (2014) at a 4-km grid resolution. An existing 12-km CMAQ model

of Western US is employed to provide boundary conditions for the new model. The model

domain is centered on the NAS Transboundary region, and includes nearly all of Washington

State and the Fraser Valley in Canada. Bi-directional CMAQ ammonia flux will be presented

from simulations that couple the USDA EPIC model which provides estimates of agricultural

fertilizer application form, timing and amount based on the NLCD2011 land use classification

and USDA regional cropping and agricultural management patterns, with the CMAQ model.

The information on cross-boundary N inputs to the landscape will be coupled with stream and

groundwater monitoring data and existing knowledge to estimate the N residual in the watershed

and N transport out of the watershed. Results will inform N management in the search for the

environmentally and economically viable and effective solutions. The NAS Transboundary

Region study is one of seven international demonstration projects contributing knowledge of

regional N budgets and collaborative approaches toward N management as part of the

International Nitrogen Management System (INMS).

1EPA, Schwede.Donna@epa.gov 2EPA, cooter.Ellen@epa.gov 3National Research Council, lin.jiajia@epa.gov 4EPA, compton.Jana@epa.gov 5USGS, jill_baron@usgs.gov

33

Episodic Acidification in the Adirondack Region of New York: Spatial

Patterns and Evidence of Recovery

Douglas Burns1, Gregory Lawrence

2, Timothy Sullivan

3, Charles Driscoll

4, Shuai

Shao5 and Todd McDonnell

6

Episodic acidification occurs when the pH and ANC of surface waters temporarily decrease

during rain events and snowmelt. The principal drivers of episodic acidification are increases in

sulfuric acid, nitric acid, organic acids, and dilution of base cations. In regions where surface

waters are sensitive to acid deposition, episodic acidification may result in several days to weeks

when ANC values may approach or decline below 0 µeq/L, a threshold below which increases in

monomeric aluminum concentrations become evident, which may result in deleterious effects to

sensitive aquatic biota. The Adirondack Mountains of New York is a region with abundant

streams and lakes, many of which are highly sensitive to the effects of acid deposition. Long-term

monitoring data indicate that pH and ANC in regional surface waters are increasing in response

to decreases in the acidity of atmospheric deposition that result from decreasing SO2 and

NOx emissions as the Clean Air Act and its ancillary rules and amendments have been

implemented. Most surface-water monitoring focuses on low-flow and broad seasonal patterns,

and less is known about how episodic acidification has responded to emissions decreases. We are

exploring spatial and temporal patterns in episodic acidification through analysis of stream

chemistry from surveys that target varying flow conditions as well as data from a few long-term

intensively sampled stream monitoring sites. Each stream sample is assigned a flow percentile

value based on a resident or nearby gage, and a statistical relation between ANC values and flow

percentile is developed. The magnitude of episodic decreases in ANC increases as low-flow ANC

increases, a pattern that likely results from an increasing influence of dilution, especially evident

when low-flow ANC values exceed 100 µeq/L. Chronically acidic streams with low-flow ANC

near 0 µeq/L show little episodic acidification, whereas streams with low-flow ANC values of

about 50 µeq/L generally show ANC decreases to less than 0 µeq/L at high flow. Preliminary

analysis of a 24-yr data set (1991-2014) at Buck Creek near Inlet, NY indicates that high-flow

ANC has recovered twice as much as low-flow ANC, and values generally no longer decline

below 0 µeq/L at the highest flows, which typically occur during spring snowmelt. Further

analyses will explore how the drivers of episodic acidification vary across the region with low-

flow ANC and whether clear trends are evident in the influence of these drivers over the past few decades.

1U.S. Geological Survey, daburns@usgs.gov 2U.S. Geological Survey, glawrenc@usgs.gov 3E&S Environmental, tim.sullivan@esenvironmental 4Syracuse Univ., ctdrisco@syr.edu 5Syracuse Univ., sshao@syr.edu 6E&S Environmental, todd.mcdonnell@esenvironmental

34

35

TECHNICAL SESSION 3:

AIR & WATER QUALITY: LINKAGES AND

SYNERGIES (CONTINUED)

Session Chairs: Mark Nilles and Helen Amos,

USGS and US EPA

Session Moderator: Rich Pouyat, USDA Forest

Service

36

37

Changes in Stream Chemistry at High Flow during 23 Years of Decreasing Acid

Deposition in the Catskill Mountains of New York

Michael McHale1, Douglas Burns

2, Jason Siemion

3 and Michael Antidormi

4

The Catskill Mountains of New York is a region with demonstrated sensitivity to acid rain. The

headwaters of the Neversink River basin are the most sensitive waters in the region with both

chronically and episodically acidic streams. High-flow events (storms and snowmelt) cause sharp

reductions in acid neutralizing capacity (ANC) and increases in nitrate (NO3-) and inorganic

monomeric aluminum (Alim). Even as streams recover from chronic acidification because of

reductions in acidic deposition, episodic acidification may continue to cause sharp declines in

ANC and increases in NO3-NO3- and Alim that can have deleterious effects on stream

ecosystems. We examined changes in stream chemistry throughout a 23 year period of decreasing

acid deposition across all flow conditions, with particular emphasis on examining changes during

high flow. Our results indicate that both chronically and episodically acidic streams are

improving at similar rates and that trends were similar between high flow and all flow conditions.

Initially we focused on spring snowmelt; we computed Mann-Kendall trends for stream

chemistry during April of each year because April is the month during which peak spring

streamflow typically occurs in this region. We found that ANC and sulfate (SO42-) trends were of

similar magnitude and direction between April-only and annual seasonal-Kendall trends.

Furthermore, the most acidic stations showed the largest recovery from acidification during

spring melt. In fact the only significant Alim April trends occurred at the 2 most acidic stations. In

general, there were fewer significant trends in chemistry during April compared to the entire year

at every station and there were no significant trends that changed direction between the April and

annual trends. We also compared annual flow-weighted mean solute concentrations at low flow,

high flow, and all flow conditions to examine whether the recovery documented by seasonal-

Kendall and the April Mann-Kendall trend analyses was apparent across flow conditions. The

greatest increases in ANC from the beginning of the study period to the end of the study period

were measured during high flow. The decrease in the number of acid episodes resulted in a

decrease in Alimconcentrations at high flow. Perhaps the most important finding was that the

frequency and magnitude of acidic episodes has decreased dramatically at the most acidic station

and Alim concentrations have decreased considerably during acidic episodes.

1U.S. Geological Survey, mmchale@usgs.gov 2U.S. Geological Survey, daburns@usgs.gov 3U.S. Geological Survey, jsiemion@usgs.gov 4U.S. Geological Survey, mantidormi@usgs.gov

38

Evaluating Potential Water Quality Impairments on National Forest Priority

Watersheds Using Estimates of Atmospheric Deposition

David Levinson1, Anita Rose

2 and Rich Pouyat

3

The U.S. Forest Service Watershed Condition Framework (WCF) is a nationally consistent

reconnaissance-level approach for assessing and classifying watershed condition, using a

comprehensive set of 12 indicators that are surrogate variables representing the underlying

ecological, hydrological, and geomorphic functions and processes that affect watershed

condition. Primary emphasis of the WCF is on aquatic and terrestrial processes and

conditions that Forest Service management activities have on stream, riparian and aquatic

habitat. As part of the WCF, National Forests designate “Priority Watersheds” where a

variety of land management treatments are planned and implemented. One of the primary

aquatic indicators of the WCF is water quality, but measuring and monitoring water quality

impacts has been difficult since many of the almost 300 Priority Watersheds are located in

headwater regions on National Forests. Initial steps are under way to collocate both water

and air monitoring on Priority Watersheds, to improve understanding of water quality

impairments due to atmospheric deposition. A primary question is understanding when air

deposition is coupled with water quality, and when they are decoupled, and why? A

specific concern is Nitrogen (N) deposition, since it impacts large parts of the U.S., and

initial efforts will be to use N deposition estimates to identify a subset of Priority

Watersheds with potential water quality impairments for collocating air and water monitoring.

1US Forest Service, dlevinson@fs.fed.us 2US Forest Service, anitarose@fs.fed.us 3US Forest Service, rpouyat@fs.fed.us

39

Integration of Atmospheric Deposition and Water Quality Monitoring in the El

Yunque National Forest, Puerto Rico

Anita K. Rose1, Richard Pouyat

2, Linda Geiser

3, David Levinson

4, Chelcy Miniat

5,

Bret A. Anderson6, Helen M. Amos

7 and Denice Shaw

8

Excess levels of nutrients (nitrogen and phosphorus) in surface water are associated with

increased biological stress and decreased biological diversity. There is a significant need to

enhance connections between atmospheric deposition monitoring and surface water quality

monitoring to better understand linkages between air quality and the health of aquatic

ecosystems. The limited integrated air/water monitoring we currently have is almost exclusively

concentrated in temperate latitudes. El Yunque National Forest, Puerto Rico offers a unique

opportunity to investigate air/water linkages because (1) watershed N/P loads are dominated by

atmospheric inputs, (2) it already has an NADP super site, and (3) it is a tropical rainforest that

experiences frequent, intense convective storms that are major source of lightning NOx. As part

of WADeIn (Water Quality & Atmospheric Deposition Integration) -- an interagency

collaboration improving the coordination and integration of atmospheric deposition and surface

water quality monitoring to fill critical knowledge gaps about the sources, transport, and impacts

of N and P -- the USDA Forest Service is proposing to install real-time water quality sensors for

nutrients in the El Yunque National Forest. The goal is to integrate the resulting data with those

from the NADP super site that currently exists in the National Forest. This pilot study will

demonstrate the usefulness of the selected water sensors for quantification of nutrients in stream

and provide quantitative information about how closely coupled stream nutrient exports are to

atmospheric inputs. The window of opportunity for the El Yunque pilot is very timely and will be

able to leverage a number of other pilots launching on similar timelines by other agencies and

organizations. Additional benefits of the El Yunque pilot include: outreach to the local

community through the El Yunque National Forest visitor center; test usefulness of sensors to be

deployed as part of the recently established Watershed Condition Framework; foster

collaborations between the Forest Service’s National Forest System and Research and

Development branches, EPA, NOAA, and USGS. Results from this pilot study will provide an

opportunity to further explore integrated air/water quality monitoring, as well as provide a much

needed investigation into the status of watershed/water quality in the El Yunque National Forest.

1USDA Forest Service, anitarose@fs.fed.us 2USDA Forest Service, rpouyat@fs.fed.us 3USDA Forest Service, lgeiser@fs.fed.us 4USDA Forest Service, dlevinson@fs.fed.us 5USDA Forest Service, cfminiat@fs.fed.us 6USDA Forest Service, baanderson02@fs.fed.us 7EPA, amos.helen@epa.gov 8EPA, shaw.denice@epa.gov

40

41

TECHNICAL SESSION 4:

DEPOSITION MODELING AND MONITORING

Session Chairs: Anne Rea and Eric Prestbo,

USDA Forest Service and Tekran

42

43

Evaluation of Wet Atmospheric Deposition along the Coast of the Gulf

of Mexico: An International Collaboration Opportunity

Rodolfo Sosa E.1, Humberto Bravo A.

2, Ana Luisa Alarcon J.

3, Maria del Carmen

Torres B.4, Pablo Sanchez A.

5, Monica Jaimes P.

6, Elias Granados H.

7, David

Gay8, Christopher Lehmann

9 and Gregory Wetherbee

10

The evaluation of atmospheric deposition at regional scales requires international collaboration to adequately characterize the occurrence of potential impacts and establish measures to mitigate them. The central theme

for the 2017 NADP Meeting, “NADP data: making the world a better place, one monitor, one network, one

study at time,” gives us the direction to evaluate atmospheric deposition in the Gulf of Mexico Region.

The Gulf of Mexico Region has important sources of acid rain precursors, both on land and at sea, located in

countries bordering the region, such as the USA, Mexico and Cuba. It is very important to study the chemical composition of atmospheric wet deposition through international cooperation. Studies on the Mexican coast

have recorded the presence of acid rain since 2003. The aim of this study was to evaluate the major ions (Na+,

NH4+, K+, Mg2+, Ca2+, SO4

2-, NO3- and Cl-), pH and conductivity in atmospheric wet deposition, collected

daily from 2003 to 2015 at a sampling site located along the coast of Mexico (La Mancha, Veracruz) and

compare the values with the NADP sampling sites located along the Gulf of Mexico coast from Texas to

Florida.

Among the major findings: all ions were present in greater levels in “La Mancha” in comparison with each

one of the sampling sites in the USA, with exception of nitrogen compounds (NO3- and NH4

+ ), which were comparable to the USA sites. The levels of sulfates in Mexico were comparable to the highest US NADP

sites. The ratio of SO42- to NO3

- has been used as indicator of the effectiveness of SO2 and NOx emissions

reductions in the USA. The SO42-/NO3

- ratio found for “La Mancha” in 2015 was 4.8, the highest value when compared to other sites in the Gulf of Mexico, which had ratios between 1.03 and 1.87. Due to the high levels

of SO42- and the ratio SO4

2-/NO3- found at “La Mancha,” it is important to monitor the sulfur dioxide emission

sources in Mexico.

In addition to “La Mancha” sampling site, two additional sampling sites, in Mexico, have recently been

incorporated to the atmospheric deposition study: one in the City of Campeche and another in the Port of Veracruz. Initial results from these sites will be shown.

The establishment of the international network for the evaluation of atmospheric deposition in the Gulf of Mexico represents a great opportunity for international collaboration. NADP protocols for sampling and

analysis will be adopted, including quality-assurance and quality-control protocols, to ensure that information

generated is comparable between current participating countries, USA and México and possibly Cuba.

1Universidad Nacional Autonoma de Mexico (UNAM), rodsosa@unam.mx 2UNAM, hbravo@unam.mx 3UNAM, ana.alarcon@atmosfera.unam.mx 4UNAM, mcarmen@atmosfera.unam.mx 5UNAM, pasa@unam.mx 6UNAM, mjaimes@sedema.cdmx.gob.mx 7UNAM, elias78@unam.mx 8National Atmospheric Deposition Program (NADP), dgay@illinois.edu 9NADP, clehmann@illinois.edu 10United States Geological Survey, wetherbee@usgs.gov

44

Methylmercury and Total Mercury in Marine Stratus Cloud and Fog Water:

Sources, Sinks, and Lifetimes

Peter Weiss-Penzias1, Kenneth Coale

2, Wes Heim

3, Armin Sorooshian

4, Hossein

Dadashazar5, Alex MacDonald

6, Zhen Wang

7, Ewan Crosbie

8, Haflidi

Jonsson9 and Jerry Lin

10

Monomethylmercury (MMHg) concentrations in marine stratus cloud and fog water in California

are enhanced to upwards of 1 ng L-1 compared to concentrations typically found in rain water,

which are closer 0.1 ng L-1. This raises the possibility that coastal terrestrial ecosystems

impacted by marine fog and clouds could be exposed to this potent neurotoxin. Efforts to

measure MMHg in cloud and fog water on the California coast indicate that the source of MMHg

is from evasion of dimethylmercury (DMHg) and subsequent demethylation in the air or in the

droplet to form MMHg. This presentation will highlight the data collected on land, at sea, and by

aircraft at numerous locations in coastal California since 2014, and discuss the major gaps in our

understanding of the cycling and transport of methylated Hg compounds in the oceanic mixed layer, atmospheric marine boundary layer, and the cloud droplet.

1University of California, Santa Cruz, pweiss@ucsc.edu 2Moss Landing Marine Labs, coale@mlml.calstate.edu 3Moss Landing Marine Labs, wheim@mlml.calstate.edu 4University of Arizona, armin@email.arizona.edu 5University of Arizona, hosseind@email.arizona.edu 6University of Arizona, abmacdonald@email.arizona.edu 7University of Arizona, zhenw@email.arizona.edu 8NASA UNIVERSITIES SPACE RESEARCH ASSOCIATION, ewan.c.crosbie@nasa.gov 9Naval Postgraduate School, hjonsson@nps.edu 10Lamar University, lincx@lamar.edu

45

Trends in NADP Bromide Wet Deposition Concentrations, 2001-2016

Gregory Wetherbee1, Christopher M.B. Lehmann, Ph.D.

2, Lee A. Green

3, Mark F.

Rhodes4, Brian M. Kerschner

5 and Amy S. Ludtke

6

Bromide (Br-) and other solute concentration data from wet deposition samples collected by the

National Atmospheric Deposition Program (NADP) from 2001 to 2016 (study period), were

analyzed for statistical trends both geographically and temporally and by precipitation type.

Bromide was more frequently detected at NADP sites in coastal regions of the continental United

States. The Br- concentration data set was characterized by greater than 86 percent of sample

concentrations below analytical detection. Analysis revealed that Br- concentrations were higher

in rain (only) versus precipitation containing snow. Decreasing Br- wet deposition concentrations

were observed at a majority of NADP sites over the study period; approximately 25 percent of

the trend slopes were statistically significant at the alpha=0.10 level. Correlations between Br-,

Cl-, and NO3- concentrations were evaluated to investigate sea-salt as a Br-source and potential

Br- oxidation of atmospheric nitrite (NO2(g)) to NO3-(aq).

Potential causes for decreasing Br- concentrations were explored, including annual and seasonal

changes in precipitation depth, reduced emissions of methyl bromide (CH3Br) from coastal

wetlands, and declining industrial use of bromine compounds. Trend analyses indicated that

precipitation depth generally increased during the study period at the majority of NADP sites,

which diluted Br- below analytical detection in many samples. Declining Br- concentrations also

are consistent with declining industrial CH3Br emissions mandated by the Montreal Protocol.

Chemical processes that deplete Br- from sea-salt aerosols and inundation of saltmarsh habitat

suggest changing marine conditions were identified as possible influences on temporal trends in

Br- concentrations. There are no known ecological consequences of changing Br- concentrations

in wet deposition at this time, but the trends may help to explain the chemistry of pollutants like CH3Br and the changing chemical climate of the atmosphere.

1U.S. Geological Survey, wetherbe@usgs.gov 2Univ. Illinois, Prairie Research Institute, ISWS, clehmann@illinois.edu 3Univ. Illinois, Prairie Research Institute, ISWS, leegreen@illinois.edu 4Univ. Illinois, Prairie Research Institute, ISWS, rhodes1@illlinois.edu 5Univ. Illinois, Prairie Research Institute, ISWS, bmkersch@illinois.edu 6U.S. Geological Survey, asludtke@usgs.gov

46

Total Deposition by Measurement-model Fusion using ADAGIO

Amanda Cole1, Alain Robichaud

2, Mike Moran

3, Mike Shaw

4, Alexandru Lupu

5,

Marc Beauchemin6, Guy Roy

7, Vincent Fortin

8 and Robert Vet

9

Environment and Climate Change Canada’s ADAGIO project (Atmospheric Deposition Analysis

Generated by optimal Interpolation from Observations) generates maps of wet, dry and total

annual deposition of oxidized and reduced nitrogen (N) and sulphur (S) in Canada and the United

States by fusion of observed and modeled data. Optimal interpolation methods are used to

integrate seasonally-averaged surface concentrations of gaseous, particulate, and precipitation

species into concentration fields predicted by Environment and Climate Change Canada’s in-line

regional air quality model GEM-MACH (Global Environmental Multiscale model - Modelling

Air quality and Chemistry). The result, a product called objective analysis (OA), corresponds to

an interpolation of the difference between the modeled and measured values at network

observation sites. Gas and particulate OA concentration fields are then combined with effective

deposition velocities from GEM-MACH to calculate dry deposition. Similarly, OA

concentrations of precipitation ions are combined with precipitation amounts from the Canadian

Precipitation Analysis (CaPA) to calculate wet deposition. CaPA is also an objective analysis

where all available precipitation data sets are fused with precipitation amounts predicted by

GEM. Results from the 2010 development year are compared with previously-generated wet

deposition kriging maps, results from the US EPA’s Total Deposition (TDEP) method, and

independent validation performed with surface measurements not used in the analysis where available.

1Environment and Climate Change Canada, amanda.cole@canada.ca 2Environment and Climate Change Canada, alain.robichaud@canada.ca 3Environment and Climate Change Canada, mike.moran@canada.ca 4Environment and Climate Change Canada, mike.shaw@canada.ca 5Environment and Climate Change Canada, alexandru.lupu@canada.ca 6Environment and Climate Change Canada, marc.beauchemin@canada.ca 7Environment and Climate Change Canada, guy.roy@canada.ca 8Environment and Climate Change Canada, vincent.fortin@canada.ca 9Environment and Climate Change Canada, robert.vet@canada.ca

47

TECHNICAL SESSION 5:

URBAN AIR QUALITY AND DEPOSITION

Session Chair: Steven Decina,

Boston University

48

49

Quantifying Urban Nitrogen Emission and Deposition Through Optical

Sensing Techniques

Kang Sun1

As the third most abundant nitrogen species in the atmosphere, ammonia (NH3) is a key

component of the global nitrogen cycle. Since the industrial revolution, humans have more

than doubled the emissions of NH3 to the atmosphere by industrial nitrogen fixation,

revolutionizing agricultural practices, and burning fossil fuels. Ammonia is a major

precursor to fine particulate matter (PM2.5), which has adverse impacts on ecosystem and

human health. On-road vehicles are key sources of NH3 emissions and depositions in urban

areas. Due to the successful control of oxidized nitrogen (NOx) emissions and the lack of

NH3emission control, new vehicles manufactured now emit more NH3 molecules than

NOx molecules. To quantify NH3 emissions at an urban scale, a quantum cascade laser-

based NH3 sensor was integrated into a mobile laboratory, which participated in extensive

field campaigns, including the NASA DISCOVER-AQ campaigns and the CAREBeijing-

NCP campaign in China (400 h on-road time, 18,000 km total sampling distance). Vehicle

NH3:CO2 emission ratios in the U.S. are found to be similar between cities (0.33–0.40

ppbv/ppmv, 15% uncertainty) despite differences in fleet composition, climate, and fuel

composition. While Beijing, China has a comparable emission ratio (0.36 ppbv/ppmv) to

the U.S. cities, less developed Chinese cities show higher emission ratios (0.44 and 0.55

ppbv/ppmv). If the vehicle CO2 inventories are accurate, NH3 emissions from U.S. vehicles

(0.26 ± 0.07 Tg/yr) are more than twice those of the National Emission Inventory (0.12

Tg/yr). Vehicle NH3 emissions are greater than agricultural emissions (which is highly

uncertain as well) in counties containing near half of the U.S. population and require

reconsideration in urban air quality models. Future opportunities of characterizing

NH3 emissions and investigating the transition of NH3/NOx regimes at the global scale enabled by satellite observations will also be discussed.

1Harvard-Smithsonian Center for Astrophysics, kang.sun@cfa.harvard.edu

50

Using Moss to Detect Fine-Scaled Deposition of Heavy Metals in Urban

Environments

Sarah Jovan1, Geoffrey Donovan

2, Demetrios Gatziolis

3, Vicente Monleon

4 and

Michael Amacher5

Mosses are commonly used as bio-indicators of heavy metal deposition to forests. Their

application in urban airsheds is relatively rare. We used moss to develop fine-scaled, city-

wide maps for heavy metals in Portland, Oregon, to identify pollution “hotspots” and serve

as a screening tool for more effective placement of expensive air quality monitoring

instruments. In 2013 we measured twenty-two elements in epiphytic moss sampled on a

1km x1km sampling grid (n = 346). We detected large hotspots of cadmium and arsenic in

two neighborhoods associated with stained glass manufacturers. Air instruments deployed

by local regulators to moss-detected hotspots measured cadmium concentrations 49 times

and arsenic levels 155 times the state health benchmarks. Moss maps also detected a large

nickel hotspot near a forge where air instruments later measured concentrations 4 times the

health benchmark. In response, the facilities implemented new pollution controls, air

quality improved in all three affected neighborhoods, revision of regulations for stained

glass furnace emissions are underway, and Oregon’s governor launched an initiative to

develop health-based (vs technology-based) regulations for air toxics in the state. The moss

maps also indicated a couple dozen smaller hotspots of heavy metals, including lead,

chromium, and cobalt, in Portland neighborhoods. Ongoing follow-up work includes: 1)

use of moss sampling by local regulators to investigate source and extent of the smaller

hotspots, 2) use of lead isotopes to determine origins of higher lead levels observed in moss

collected from the inner city, and 3) co-location of air instruments and moss sampling to

determine accuracy, timeframe represented, and seasonality of heavy metals in moss.

1U.S. Forest Service Pacific Northwest Research Station, sjovan@fs.fed.us 2U.S. Forest Service Pacific Northwest Research Station, gdonovan@fs.fed.us 3U.S. Forest Service Pacific Northwest Research Station, dgatziolis@fs.fed.us 4U.S. Forest Service Pacific Northwest Research Station, vjmonleon@fs.fed.us 5U.S. Forest Service, retired, mcamacher1@outlook.com

51

Elemental Carbon Deposition to Urban Tree Canopies: Magnitudes and Spatial

Patterns

Alexandra G. Ponette-González1, Tate E. Barrett

2, Jenna E. Rindy

3 and Rebecca J.

Sheesley4

Urban areas are a major source of atmospheric elemental carbon (EC), a component of fine

particulate matter and a powerful climate-forcing agent. However, empirical

measurements of EC removal from urban atmospheres by wet and dry deposition are few in

number and virtually none explicitly quantify intra-urban variability in deposition rates.

Tree canopies are likely important sinks for EC on the cityscape because of their

propensity to scavenge suspended particulate matter, of which EC can be a significant

component in urban settings. This research aims to quantify magnitudes and spatial

patterns of total (wet + dry) EC deposition to urban tree canopies in the Dallas-Fort Worth

Metroplex using the throughfall method (collection of water that falls from the canopy to

the forest floor). In March 2017, we established 41 throughfall collectors across a 51

km2 area in the City of Denton, Texas. Collectors were deployed beneath 22 post oak

(Quercus stellata) and 19 live oak (Quercus virginiana) trees in residential yards and urban

greenspaces, both near (≤100 m) and far from roads (>100 m) with truck traffic.

Additionally, 16 bulk rainfall samplers were established in grassy areas with no canopy

cover. Throughfall and rainfall are currently being sampled on an event basis. Total EC

deposition to urban tree canopies measured during a single rainfall event in May 2017

ranged widely, from 0.12 to 5.6 mg m-2. On average, EC deposition to post oak canopies

was more than 2-fold higher (1.8 ± 2.0 (SD) mg m-2) compared to live oak canopies (0.67 ±

0.27 mg m-2) whereas bulk rainfall deposition was 0.077 ± 0.11 mg m-2. Our preliminary

findings show that oak trees are effective urban air filters, removing up to 23 times more

EC from the atmosphere than rainwater alone. Qualitative observations suggest that tree

size and density of emissions sources within a 50-m radius buffer also contribute to spatial

variability in EC deposition. Resolving surface controls on atmospheric EC removal is key to developing and assessing climate and air quality mitigation strategies.

1Department of Geography and the Environment, University of North Texas,

alexandra@unt.edu 2Department of Geography and the Environment, University of North Texas,

Tate.Barrett@unt.edu 3Department of Geography and the Environment, University of North Texas,

Jenna.Rindy@unt.edu 4Department of Environmental Science, Baylor University, Rebecca_Sheesley@baylor.edu

52

Characteristics and Ecological Impacts of Atmospheric Deposition in Urban

and Urban-Affected Regions

Mark Fenn1, Andrzej Bytnerowicz

2, Susan Schilling

3, Michael Bell

4 and James

Sickman5

Urban air pollution causes major effects on human and ecosystem health and the environment.

On-road emissions are major drivers of air quality in urban regions. Technologies for reducing

NOx emissions result in production of reduced forms of N. Industrial, urban and on-road

emissions of NOx have declined dramatically while NH3 emissions have increased. Simulation

models underestimate NH4+ deposition, and models and regional monitoring networks do not

capture fine-scale spatial heterogeneity in dry deposition or fogwater deposition to receptor sites

affected by urban emissions. The highest N deposition reported for the Western hemisphere (70

kg/ha/yr as throughfall) occurs in the San Bernardino National Forest within the eastern region of

the Los Angeles Air Basin. Deposition can vary ten-fold over a 50-60 km gradient in forests

downwind of Los Angeles. Contrary to previous assumptions, sulfur deposition in Los Angeles

remains unusually high (30-40 kg/ha/yr), due to emissions from shipping, heavy transport and

industry. Wet deposition data are of limited utility in characterizing deposition in arid regions.

Notwithstanding, long-term data at the NADP site near Los Angeles (CA42) indicate decreasing

temporal trends in deposition of SO42+ and NO3

- and slightly increasing trends in NH4+. At

several such urban-dominated NADP sites across the U.S., wet deposition switched to

NH4+ values that are consistently greater than NO3

- molar values during the 2005 to 2010 period.

Data on urban NH3 concentrations support this trend of increasing importance of reduced forms

of N, primarily from on-road emissions of NH3. In this light, the Lake Tahoe Air Basin case

study will also be discussed.

Nitrogen critical loads in ecosystems of highly-urbanized southern California have been

determined for streamwater NO3-, epiphytic lichen community change, vegetation type change,

tree health, soil acidification and mycorrhizal responses. Urban emissions have resulted in

extensive areas of CL exceedance, although agricultural emissions are also important in some

locations. Urban emissions of N from Mexico City have likewise caused eutrophication impacts

to forested catchments in the air basin of this megacity. Ecosystems downwind of Mexico City

and Los Angeles are also exposed to phytotoxic levels of ozone---thus multipollutant effects are

important in evaluating ecosystem responses to urban air pollution. Urban air pollution affects

ecosystem services within the urban environment and in wildland ecosystems located within the

path of urban and transport corridor plumes. Impacted services include the provision of clean

drinking water and aesthetic, residential and recreational use of forests and other vegetation

types.

1USDA Forest Service, PSW Research Station, mfenn@fs.fed.us 2USDA Forest Service, PSW Research Station, abytnerowicz@fs.fed.us 3USDA Forest Service, PSW Research Station, sschilling@fs.fed.us 4National Park Service, Air Resources Division, michael_d_bell@nps.gov 5University of California, Riverside, Department of Environmental Sciences, james.sickman@ucr.edu

53

Assessing Sources and Fluxes of Reactive Nitrogen Deposition to Urban

Landscapes Using Ion Exchange Resins

Rebecca Forgrave1, Kassia Groszewski

2, Elizabeth Boyer

3 and Emily Elliott

4

Previous research documents that urban reactive nitrogen deposition is both higher than rural

areas and spatially variable, highlighting key knowledge gaps in understanding the sources,

dynamics, and overall fluxes of reactive nitrogen deposition in urban areas. Traditional methods

used by the NADP NTN and US EPA CASTNET, for wet and dry deposition fluxes respectively,

require considerable cost to establish and maintain, thus making it difficult to establish enough

sites to fully explore this phenomenon or spatial variability. Ion exchange resins, however, offer

a robust alternative as they are relatively inexpensive, integrate fluxes over many weeks without

requiring exact precipitation volume, and can be used for isotopic analyses of resin eluents

without fractionation. In this project, ion exchange resin columns selectively targeting nitrate

(NO3-) or ammonia (NH4

+) were deployed at 7 monitoring sites (5 urban and 2 rural) around

Pittsburgh and the nearest NTN-CASTNET site and were exchanged every 1-2 months over a

one-year period. Column eluents were analyzed for concentrations of NO3- and NH4

+ to calculate

deposition fluxes, as well as dual nitrate isotopes (δ15N, δ18O) to examine emission sources and

oxidation chemistry. Fluxes were compared to those recorded by NTN and CASTNET at the

nearest rural national monitoring sites to verify that the ion exchange resins are capturing the

same signal as the established networks. Contrary to previous research, preliminary results

indicate no significant differences in deposition fluxes between urban and rural sites for either

NO3- or NH4

+. δ15N and δ18O values of eluted NO3- were highly variable among network sites

where both δ15N and δ18O values are generally higher in winter than summer. The range in δ15N

and δ18O values and the seasonal patterns are consistent with prior reports linking temporal

patterns in δ15N with increased power plant emissions during the winter months and δ18O value

with seasonal changes in oxidation chemistry. This research seeks to narrow existing knowledge

gaps regarding the fluxes of reactive nitrogen deposition to landscape, and how the high degree

of spatial variability observed in urban systems is related to NOX and NH3 emission sources. The

preliminary results reported here demonstrate the need for finer spatial scale sampling to further

understand causes of site variability, as well as the potential for ion exchange resins to be used as

a tool for this type of analysis.

1University of Pittsburgh, ref61@pitt.edu 2University of Pittsburgh, klg83@pitt.edu 3Penn State University, ewb100@psu.edu 4University of Pittsburgh, eelliott@pitt.edu

54

Increasing Ethanol Consumption as a Renewable Fuel: How Will Vehicle

Ethanol Emissions Impact the Urban Atmosphere?

J. David Felix1, Rachel Thomas

2, Matt Casas

3, Megumi Shimizu

4, G. Brooks

Avery5, Robert Kieber

6, Ralph Mead

7, Joan Willey

8 and Chad Lane

9

US ethanol fuel consumption has increased exponentially over the last two decades as part of a

movement to reduce greenhouse gas emissions and become more fuel independent. US annual

renewable fuel production is ~16 billion gallons and is required to increase to 36 billion

according to the renewable fuel standard. Regardless of the technology or feedstock used to

produce renewable fuel, the primary end product will be ethanol. This has spurred extensive

debate among a diverse array of US stakeholders about the practicality of the renewable fuel

standard. Much of the evidence for both sides of the debate relies on the life cycle analysis of

ethanol production and weighing the effects of ethanol production on our economy, environment,

and food and water supply. However, one principal uncertainty not adequately addressed by

either side in this debate is “What are the impacts of increasing ethanol fuel consumption and

subsequently ethanol and aldehyde emissions on atmospheric composition and chemistry?” This

is despite modeling efforts that predict increases in blended fuel consumption will increase

national average ozone concentrations. This is especially true for urban air sheds consisting of

blended fuel vehicle emissions that result in elevated concentrations of VOCs with relatively high

ozone reactivities (i.e. aldehydes, alcohols).

The presented work provides evidence of high ethanol atmospheric concentrations associated

with densely populated urban areas and ethanol refineries throughout the globe by measuring wet

deposition ethanol concentrations. This has also produced the first global deposition flux of

ethanol (2.4± 1.6 Tg/yr) based on empirical data and suggests wet deposition removes 6 to 17%

of atmospheric ethanol annually. To provide further evidence of the increasing anthropogenic

sources leading to higher atmospheric ethanol concentrations, a method to measure the carbon

isotopic composition of ethanol at natural abundance levels was developed and carbon isotope

signatures (δ13C) of vehicle ethanol emission sources are reported for both Brazil (-12.7‰) and

the US (-9.8‰). An isotope mixing model using vehicle and biogenic endmembers was used to

estimate ethanol source apportionment in wet deposition and results suggest anthropogenic

sources contribute up to 7X more ethanol than previously predicted in modeled ethanol

inventories. With the US renewable fuel standard requiring a substantial increase in the next five

years, it is essential that the entities involved in deciding the fate of US fuel consumption have

knowledge of all the advantages and disadvantages of increased ethanol consumption, including

the atmospheric impacts of ethanol fuel emissions.

1Texas A&M University - Corpus Christi, joseph.felix@tamucc.edu 2Florida State University, rt16d@my.fsu.edu 3University of North Carolina Wilmington, msc4317@uncw.edu 4University of North Carolina Wilmington, shimizum@uncw.edu 5University of North Carolina Wilmington, averyg@uncw.edu 6University of North Carolina Wilmington, kieberr@uncw.edu 7University of North Carolina Wilmington, meadr@uncw.edu 8University of North Carolina Wilmington, willeyj@uncw.edu 9University of North Carolina Wilmington, lanec@uncw.edu

55

TECHNICAL SESSION 6:

NITROGEN: TRANSPORT DEPOSITION AND

EFFECTS

Session Chair: Justin Valliere

University of California Los Angeles

56

57

Ecosystem Flip-Flops in Response to Anthropogenic N Deposition: The

Importance of Long-term Experiments

George Vourlitis1

Anthropogenic nitrogen (N) deposition has the capacity to alter terrestrial ecosystem structure

and function; however, short-term (months-years) responses may be fundamentally different than

long-term (years-decades) responses. Here the results of a 14 year field N addition experiment

are reported for two semi-arid shrublands, a post-fire chaparral and a mature coastal sage scrub

(CSS), located in San Diego County, California that have been exposed to 50 kgN ha-1 yr-1 since

2003. Since >90% of the anthropogenic N in this region consists of dry deposition, N was added

during the late-summer or early-fall each year to assess how dry N inputs alter ecosystem

processes. Both shrublands experienced complete “flip-flops” in their response to experimental

dry N inputs. For example, post-fire chaparral plots exposed to added N had significantly lower

net primary production (NPP) than control plots over the first 3 years of the experiment, but

thereafter, the NPP in N plots increased consistently each year and became significantly higher

than in control plots after 7 years of N fertilization. In CSS, NPP and the abundance of Artemisia

californica, a co-dominant shrub, increased significantly in N plots over the first 6 years, but

thereafter, NPP and the abundance of A. californica and Salvia mellifera, the other co-dominant

shrub, declined, and now the N plots have a lower NPP and are dominated by the invasive

annual Brassica nigra. These transient responses, and interactions between N accumulation and

other factors such as post-fire succession (chaparral) and chronic drought (CSS), would have

been missed if the experiment was ended after the end of a typical funding cycle, highlighting the

importance of long-duration field experiments in assessing ecosystem responses to chronic N enrichment.

1California State University, georgev@csusm.edu

58

Organic Nitrogen in Aerosols at a Forest Site in Southern Appalachia

John Walker1, Xi Chen

2, Mingjie Xie

3, Michael Hays

4 and Eric Edgerton

5

This study investigates the composition of organic particulate matter (PM2.5) in a remote montane

forest in the southeastern U.S., focusing on the role of organic nitrogen (N) in sulfur-containing

secondary organic aerosol (SOA) and aerosols associated with biomass burning. Measurements

targeted four groups of compounds: 1) nitro-aromatics associated with biomass burning; 2)

organosulfates and nitrooxy organosulfates produced from biogenic SOA precursors (i.e.,

isoprene, monoterpenes and unsaturated aldehydes); 3) terpenoic acids formed from monoterpene

oxidation; and 4) organic molecular markers including methyltetrols, C-5 alkene triols, 2-

methylglyceric acid, 3-hydroxyglutaric acid and levoglucosan. Terpenoic acids and organic

markers were included to assist in characterizing the extent of biogenic compound oxidation and

atmospheric processing (i.e., aerosol aging) as well as contributions from biomass burning sources.

The average fraction of WSON in water soluble total nitrogen (WSTN) exhibited a pronounced

seasonal pattern, ranging from ~18% w/w in the spring to ~10% w/w in the fall. Nitro-aromatic

and nitrooxy-organosulfate compounds accounted for as much as 28% w/w of WSON. Oxidized

organic nitrogen species showed a maximum concentration in summer (average of 0.65ngN/m3,

maximum of 1.83ngN/m3) consistent with greater relative abundance of aged biogenic SOA

tracers (higher generation oxygenated terpenoic acids). Highest concentrations of nitro-aromatics

(eg. Nitrocatechol and methyl-nitrocatechol) were observed during the fall season associated with

aged biomass burning plumes. Isoprene derived organosulfate (MW216, 2-methyltetrol derived),

which is formed from isoprene epoxydiols (IEPOX) under low Nox conditions, was the most

abundant individual organosulfate. Although nitro-aromatics and nitrooxy organosulfates account

for a small fraction (seasonal averages of 1.0 to 4.4%) of WSON, our results provide insight into

atmospheric formation processes and sources of these largely uncharacterized organic nitrogen

species.

1US EPA, walker.johnt@epa.gov 2US EPA, chen.xi@epa.gov 3US EPA, xie.mingjie@epa.gov 4US EPA, hays.michael@epa.gov 5ARA, Inc, eedgerton@atmospheric-research.com

59

Quantifying Nitrogen Deposition Inputs and Impacts on Plant Richness in a

Mediterranean-type Shrubland

Justin Valliere1, Andrzej Bytnerowicz

2, Mark E. Fenn

3, Irina C. Irvine

4, Robert F.

Johnson5 and Edith B. Allen

6

Human activities have contributed to increased nitrogen (N) availability in terrestrial ecosystems

worldwide due to atmospheric pollution and resulting N deposition. Previous work in coastal

sage scrub (CSS) of southern California has established a clear link between elevated N

deposition and negative ecological impacts on native vegetation. However, while declines in

plant richness have been observed under high N deposition in a number of ecosystems

worldwide, studies examining this relationship in CSS are severely lacking. We measured levels

of N pollutants in the atmosphere and determined rates of N deposition across the landscape

based on atmospheric concentrations, deposition velocities of different reactive N forms, leaf area

index and plant stomatal uptake. We also measured soil N availability and plant community

composition of CSS at thirty sites across the Santa Monica Mountains in an effort to explore

relationships between plant richness and cover with atmospheric N inputs. We predicted elevated

rates of N deposition would be associated with lower plant diversity and higher cover of

nonnative species. Consistent with these hypotheses, we demonstrate that N deposition is

associated with reduced plant richness and slight increases in nonnative cover across the Santa

Monica Mountains. We also show through a number of field and greenhouse experiments that

declines in native species may be driven by changes to plant-water relations, altered plant-soil

feedbacks, and contrasting plant functional traits in native and invasive species. As human

activities continue to alter global N cycling, efforts to conserve native ecosystems will require explicit consideration of atmospheric N deposition.

1University of California Los Angeles, valliere@ucla.edu 2U.S. Forest Service, Pacific Southwest Research Station, Riverside, CA 3U.S. Forest Service, Pacific Southwest Research Station, Riverside, CA 4National Park Service, Pacific West Regional Office, San Francisco, CA 5Center for Conservation Biology University of California, Riverside, CA 6Department of Botany and Plant Sciences University of California, Riverside, CA

60

61

TECHNICAL SESSION 7:

NITROGEN: TRANSPORT DEPOSITION AND

EFFECTS (CONTINUED)

Session Chair: Justin Valliere,

University of California Los Angeles

62

63

Atmospheric Deposition Evaluation as a Tool to Preserve Urban Natural Green

Areas: Mexico City Case

María Alejandra Fonseca1, Julio Campo

2, Luis Zambrano

3, Rodolfo Sosa

4, Ana

Luisa Alarcón5, María del Carmen Torres

6, Pablo Sánchez

7, Olivia Rivera

8 and

Mónica del Carmen Jaimes9

United Nations data indicate that by the year 2030, approximately 60% of the world’s population will live in urban areas.

Within urban ecosystems, the anthropogenic pollutants emissions in the atmosphere are concentrated and intensified, mainly

linked to economic activities. Since most of these pollutants are harmful to humans, its reduction in the environment is a

topic of international, national and local interest. It is important to note that mitigating these emissions is also vital for the

conservation of urban natural green areas, which at the same time provide ecosystem services to cities.

Mexico City Metropolitan Area (MCMA) has a dynamic population of more than 20 million inhabitants being the twelfth

largest city in the world and as all megacities faces great challenges in which it refers to environmental sustainability and

quality of life of its inhabitants. Actually, MCMA has 23 urban natural green areas and a community area corresponding to

26,047 ha with ecological conservation status (it corresponds to 17.42% of the city territory of 148,500 ha) which offer

various ecosystem services such as aquifer recharge, greenhouse gas fixation, climate regulation, agricultural production,

noise control, CO2 fixation, local wildlife reservoir, both flora and fauna, and of course, and not least important, recreational

and cultural activities. That is why it is essential to evaluate the quality of the atmospheric deposition that is presented in this

megacity, to maintain the conservation and management of these natural protected areas. Fortunately, the city is provided

with a network of monitoring atmospheric deposition (REDDA) that uses semi-automatic equipment for the collection of dry

deposition and wet deposition samples at 16 sampling sites. Some of these monitoring sites are within natural urban areas.

The operation of this network is in collaboration with the Government of Mexico City with the Center for Atmospheric

Sciences of the National Autonomous University of Mexico.

The most important findings in relation of the atmospheric deposition evaluation in MCMA include:

The pH values of the samples at the stations located in the south were more acidic than the samplesfor the stations in the

north. It is important to mention that in the south part of the MCMA is where most of the urban natural green areas are

located.

These results are in line with meteorological conditions, prevailing winds blowing from the north to the south, as well as

emission sources located in the north sector.

In most study sites, annual volume weighted decreased from 2003 to 2014. For example, “Montecillos" station located in the

North in a rural area, values decreased from 7.48 in 2003 to 5.03 in 2014.

In the stations located in a rural area (“Montecillos” in the North and “Ajusco” in the South), a strong correlation was found

between NH4+ and SO42-, NO3-, and Cl-; this is likely due to their origin in soil (i.e., fertilizer use). The same concentration

trend was observed for SO42- and NO3- in the MCMZ stations; this indicates that the sources of acid rain precursors are

upwind (i.e., to the north) of the study area.

It is important to take advantage of the information generated by the existing network and, if necessary, increase the number

of sites to generate information for the integral decision-making on the quality of life of people in MCMA and the

conservation of the urban natural green areas, as well as studying the critical loads that occur in megacities with local and

global impact.

The actions described will help to establish an integral monitoring of the natural components of the urban ecosystem that

consider the potential impact of atmospheric deposition in soils, water bodies, flora and fauna, etc.

1fonseca.maalejandra@gmail.com 2Universidad Nacional Autónoma de México, jcampo@ecologia.unam.mx 3Universidad Nacional Autónoma de México, lzamgo@gmail.com 4Universidad Nacional Autónoma de México, rodsosa@unam.mx 5Universidad Nacional Autónoma de México, ana.alarcon@atmosfera.unam.mx 6Universidad Nacional Autónoma de México, maria mcarmen@atmosfera.unam.mx 7Universidad Nacional Autónoma de México, pasa@unam.mx 8SIMAT Gobierno de la Ciudad de México, orivera@sedema.df.gob.mx 9SIMAT Gobierno de la Ciudad de México, mjaimes@sma.df.gob.mx

64

Spatial and Temporal Relationships of Key Nitrogen Species between

Ambient and Deposition Regimes

Richard Scheffe1

There is increased interest in addressing adverse ecosystem effects associated with nitrogen

deposition through the secondary National Ambient Air Quality Standards (NAAQS). The

NAAQS structure raises interesting challenges in bridging ambient and deposition space while

imposing some constraints on biologically active forms of nitrogen that may not explicitly be

considered a NAAQS specie. This presentation explores two “NAAQS” bridging constructs –

transference ratios and the delineation of particulate ammonium contribution to wet deposition –

through a series of three dimensional spatial analyses across a variety of Federal Class 1 and

Ecoregion Level 3 areas based on a time series of 2002 -2012 CMAQ air quality simulations that

underpin the TDEP deposition surfaces. These analyses are used to better understand the limits

of using surface level indicators, associated with ground based monitoring systems, intended to

capture processes through the entire atmospheric column.

1U.S. EPA, scheffe.rich@epa.gov

65

Nutrient Deposition in the Headwaters of Streams may Impact Nitrogen

Loading in Southern Californian Estuaries

Pamela Padgett1, Karen McLaughlin

2 and Martha Sutula

3

As has been shown for other estuarine ecosystems, roughly a quarter of the total N and P load in Southern

California coastal waters cannot be accounted for by known anthropogenic sources. Although the contribution of deposition to estuarine nutrient loads has been demonstrated in other regions, it is has not

been well characterized in California. In particular, little data are available on the dry N and P deposition.

Studies were conducted to address the following research objectives:

1. Identify methods for measuring dry deposition controlled fumigation systems. These included

water surface samplers and acid impregnated filters and Nylasorb filters. 2. Estimate the spatial and temporal variability in N and P deposition to five, undisturbed feeder

catchments.

3. Evaluate the utility of dual isotopes: (δ18O and δ15N) to assess the contribution of atmospheric NO3

- to streams.

Of the surrogate surfaces tested in fumigation chambers, the water surface samplers produce the most reliable results for both NO3

- and NH4+. They demonstrated a strong linear relationship with air concentrations. For

the Nylasorb filters the linear relationship was weaker, and the flux of HNO3 was significantly less than to

water samplers. Citric acid impregnated filters were poor passive samplers for NH4+, but oxalic acid

impregnated filters were satisfactory under controlled fumigations. Under field conditions, the water

samplers had limited usefulness due to as evaporation and freezing, Nylasorb prove more robust under field

conditions.

The average N dry deposition was ~70% of, and the average P dry deposition is ~30% of the total load. An

important finding was that at several sites NH3+ was a more dominant N component of both wet and dry

deposition than was expected. Water surface sampler deposition data show that in general, NH4+ dry

deposition is nearly twice as high as NO3- and at some sites NH4

+ wet deposition also dominated the N

deposition pool. The prevalence of NH4+ is likely due to the proximity of agriculture even in an area of

moderately high traffic.

The high δ18O value for atmospheric NO3- across all sites suggests that the dual isotopic composition of NO3

-

could be a useful tracer for atmospheric N deposition. However, dissolved NO3- in streams did not reflect the

isotopic composition of atmospheric NO3. This was not surprising given the relatively small surface area of

headwater streams. Atmospheric deposition of nutrients is more likely indirectly accumulated in streams, following deposition to other surface before entering the streams through surface and subsurface runoff.

1USDA Forest Service, ppadgett@fs.fed.us 2Southern California Coastal Water Research Project, karenm@sccwrp.org 3Southern California Coastal Water Research Project, marthas@sccwrp.org

66

Contributions of Organic Nitrogen to the Gas Phase and Speciation of Amines in

Ambient Samples

Katherine Benedict1, Amy P. Sullivan

2 and Jeffrey L. Collett, Jr.

3

Atmospheric reactive nitrogen is a mixture of inorganic compounds like NOx, nitric acid,

ammonia, nitrate, and ammonia and organic compounds that contain nitrogen. There is

significant uncertainty in the contribution of organic nitrogen compounds to the

atmospheric reactive nitrogen budget and the deposition budget. Amines are a class of

compounds known to be present in both the gas and aerosol phase but measurements of

their abundance and speciation are limited. We have developed an ion chromatography

method using a Dionex CS19 column with conductivity detection which can speciate more

than 10 different amine compounds including the methyl and ethyl amines. A number of

amine compounds were detected in variety of ambient filter and denuder samples analyzed

and these results will be presented. The sampling efficiency of several amine compounds

will be determined. Additionally, recent papers by Matsumoto and Yamato describe a

method to determine the basic and acidic organic nitrogen contribution using a denuder

sampling technique. In this work, we test this method in the laboratory and with samples

collected in Rocky Mountain National Park. Results of laboratory testing examine

carryover between the sodium carbonate denuder used for nitric acid determination and

“acidic organic nitrogen” and the phosphorous acid coated denuder used for ammonia

determination and “basic organic nitrogen”. The contribution of “basic organic nitrogen”

and “acidic organic nitrogen” will be presented for select periods of sampling in Rocky

Mountain National Park.

1Colorado State University, kbenedic@colostate.edu 2Colorado State University, apsull@colostate.edu 3Colorado State University, Jeffrey.Collett@colostate.edu

67

TECHNICAL SESSION 8:

AMMONIA EMISSION, TRENDS, DEPOSITION

Session Chair: Katie Benedict,

Colorado State University

68

69

Investigation of Hourly Concentration Ratios of Ammonia Gas and Particulate

Ammonium at CASTNet Site in Beltsville, MD

Greg Beachley1, John T. Walker

2, Gary Lear

3 and Melissa Puchalski

4

The chemical composition of atmospheric nitrogen pollution has shifted from predominantly

oxidized nitrogenous species (particulate NO3- and gaseous NOx) to reduced inorganic nitrogen

(particulate NH4+and gaseous NH3) (Li et al., 2016, Du et al., 2014). Understanding the particle

formation chemistry and the transport of nonpoint source (i.e. fertilizer application, animal

operations) emissions is key in assessing NH3 bidirectional air-surface exchange, deposition, and

subsequent ecological impacts. Currently, national air monitoring networks are situated for

measuring integrated reduced nitrogen samples often collected for periods of a week or more.

These measurements are typically filter-based and can suffer from volatilization losses especially

for ammonium nitrate.

The EPA’s Clean Air Status and Trends Network (CASTNET) has operated co-located Monitor

for Aerosols and Gases (MARGA) online analyzers at Beltsville, MD for a long-term period

(spanning from July 2013 to July 2015 and including the Fall of 2016) in order to assess the

precision of the analyzers as well as the efficacy of co-located weekly integrated filter pack

measurements. The MARGAs hourly samples include both NH4+ and NH3 in addition to nitrate

(NO3-), sulfate (SO4

-2) and their acid gas precursors (HNO3 and SO2) and base cations (Ca+2, Na+,

Mg+2, K+). The MARGAs sampled approximately 13-months of valid data, capturing all seasons

at a site located in crop fields managed by USDA’s Agricultural Research Service. There is a

need to better understand hourly NH3:NH4+ chemistry and a need to better characterize long-term

measurements of these compounds that are deployed in national networks (CASTNET, NADP’s

AMoN, IMPROVE). This communication will explore daily and seasonal trends along with

analysis of episodic events of NH3 and NH4+ using the entire suite of MARGA measurements and

co-located meteorological measurements.

1US EPA, beachley.gregory@epa.gov 2US EPA, walker.johnt@epa.gov 3US EPA, lear.gary@epa.gov 4US EPA, puchalski.melissa@epa.gov

70

Urban and On-Road Emissions: Underappreciated Sources of Atmospheric

Ammonia

Mark Fenn1, Susan Schilling

2, Andrzej Bytnerowicz

3, Michael Bell

4, James

Sickman5, Ken Hanks

6 and Linda Geiser

7

As a result of over-reduction of nitrogen oxides, light and medium duty vehicles and newer heavy duty vehicles on U.S.

roadways emit significant levels of ammonia (NH3). Herein we provide updated spatial distribution and inventory data for

on-road NH3

emissions for the continental U.S. On-road NH3

emissions in urbanized regions are typically 0.1 – 1.3

t/km2/yr. By comparison, NH3 emissions in agricultural regions generally range from 0.4 – 5.5 t/km2/yr, with a few hotspots

as high as 6 – 11 t/km2/yr. We have identified 500 counties that receive at least 30% of the NH3

emissions from on-road

sources. Counties with higher vehicle NH3 emissions than from agriculture include 41% of the U.S. population. Within

CONUS the percent of wet inorganic N deposition from the NADP/NTN as NH4+ ranged from 37 to 83% with a mean of

59.5%. Only 13% of the NADP sites across the U.S. had less than 45% of the N deposition as NH4

+ based on data from

2014-2016, illustrating the near-universal occurrence of NH4+ deposition across the United States, regardless of the primary

sources of NH3

emissions.

In four urban sites in Oregon and Washington the NH4-N:NO

3-N ratio in throughfall averaged 1.0 (range of 0.8 – 1.3)

compared to an average ratio of 2.3 in bulk deposition (range of 1.8 – 2.9) measured in open canopy-free areas. In bulk

deposition at urban sites in the LA Basin deposition of NH4

-N and NO3-N were highly similar to each other. Ratios of NH

4-

N:NO3-N in throughfall under shrubs in the Los Angeles Air Basin ranged from 0.7 to 1.5 across a spatially extensive

network of chaparral and coastal sage scrub sites with high but varying degrees of urban influence. The NH4

-N:NO3

-N ratio

at ten sites in the Lake Tahoe Basin averaged 1.4 and 1.6 in bulk deposition and throughfall, respectively. The ratio in

throughfall at Valhalla, immediately adjacent to the city of South Lake Tahoe, was 1.9. Annual throughfall deposition and

bulk deposition of NH4-N was strongly correlated with summertime NH

3 concentrations in the Tahoe Basin. Values of

δ15NH4+ in bulk deposition and throughfall samples in the Tahoe Basin were predominantly within the range of -5.0 to -

0.9‰, indicative of tailpipe NH3

emissions. The relative importance of urban and on-road NH3 emissions versus emissions

from agriculture varies regionally. In some areas both are important and should be considered when evaluating the principal

sources of N deposition to affected ecosystems.

1USDA Forest Service, PSW Research Station, mfenn@fs.fed.us 2USDA Forest Service, PSW Research Station, sschilling@fs.fed.us 3USDA Forest Service, PSW Research Station, abytnerowicz@fs.fed.us 4National Park Service, Air Resources Division, michael_d_bell@nps.gov 5Environmental Sciences Department, University of California, Riverside, james.sickman@ucr.edu 6USDA Forest Service, PSW Research Station, bougeotte1473@yahoo.com 7USDA Forest Service, NFS-WO, Wildlife, Fish & Rare Plants, Planning, lgeiser@fs.fed.us

71

“Fingerprinting” Vehicle Derived Ammonia Utilizing Nitrogen Stable Isotopes

Wendell Walters1, Nadia Colombi

2 and Meredith Hastings

3

Ammonia (NH3) is the primary alkaline molecule in the atmosphere and plays a key role in

numerous atmospheric processes that have important implications for human health and climate

control. While agriculture activities dominate the global NH3 budget, there are large

uncertainties in the urban NH3emission inventories. The analysis of the nitrogen stable isotope

composition of NH3 (δ15N-NH3) might be a useful tool for partitioning NH3 emission sources, as

different emission sources tend to emit NH3 with distinctive δ15N signatures or “fingerprints”.

This novel tool may help improve upon urban emission inventories, which could help to improve

modeling of important atmospheric processes involving NH3. However, there is a current lack of

δ15N-NH3 measurements of potentially important urban NH3 emission sources, and many of the

reported NH3 collection methods have not been verified for their ability to accurately characterize δ15N-NH3.

Here we present a laboratory tested method to accurately measure δ15N-NH3 using honeycomb

denuders coated with a 2% citric acid solution. Based on laboratory tests, the NH3 collection

device has been optimized under a variety of conditions. Near quantitative NH3 collection is

found at a sampling rate of 10 SLPM for NH3 concentrations less than 2 ppmv, and δ15N-

NH3 precision is found to be approximately 1.0‰. This newly developed NH3 collection device

for isotopic characterization has been applied to improve our understanding of the δ15N-

NH3 signatures from vehicles. Preliminary results of NH3 collected near a road-side indicate an

average δ15N-NH3 of -2.1 ± 1.9‰. This work is ongoing, and plans are in place to collect

NH3 directly from tailpipes and from on-road air. Our preliminary results indicate that vehicle

derived NH3 has a distinctive δ15N signature compared to agricultural and waste emissions; thus,

δ15N(NH3) has the potential to be used to understand urban NH3 emission sources.

1Brown University, wendellwalters@gmail.com 2University of California Los Angeles, nkcolombi@gmail.com 3Brown University, meredith_hastings@brown.edu

72

73

POSTER SESSIONS

IN ALPHABETICAL ORDER BY AUTHOR

74

75

Measurement of Air-Surface Exchange of Speciated Nitrogen and Sulfur

Compounds in a Coastal Environment

Greg Beachley1, John T. Walker

2, Ian Rumsey

3, Mike Larsen

4, Joseph

Niehaus5 and Monica Mullis

6

Ecosystem exposure and vulnerability to atmospheric deposition of nitrogen and sulfur

compounds is assessed by the United States Environmental Protection Agency’s (U.S. EPA’s)

primary regulatory tool, the Community Multiscale Air Quality Model (CMAQ). Observational

datasets are required for the development of the dry deposition algorithms used in CMAQ. These

deposition datasets are influenced by local environmental conditions such as meteorology,

atmospheric chemistry, and surface conditions. There is a paucity of direct deposition datasets in

coastal environments, which often have different environmental conditions than inland locations.

This study builds on the previous work of Rumsey and Walker, 2016 to deploy the Monitor for

AeRosols and GAses (MARGA) to directly measure hourly fluxes of gases (NH3, HNO3, HNO2,

and SO2) and aerosols (NH4+, NO3

-, and SO42-) above a grassy field. The MARGA on-line ion-

chromatography analyzer was deployed in the same setup with two samplers at 4-m and 1-m to

directly measure concentration gradients over a grassy field in a coastal environment near

Charleston, South Carolina from mid-May through June 2017. The multi-species concentration

gradient measurements are used in conjunction with the micrometeorological aerodynamic

gradient method to determine air-surface exchange fluxes for each species to further characterize

dry nitrogen and sulfur deposition processes in a coastal environment and assess how they differ

from inland deposition processes. This communication highlights preliminary results for species

concentration gradients and meteorological data measured this summer.

1US EPA, beachley.gregory@epa.gov 2US EPA, walker.johnt@epa.gov 3US EPA, rumsey.ian@epa.gov 4College of Charleston, larsenml@cofc.edu 5College of Charleston, jdniehau@cofc.edu 6College of Charleston, mullis@g.cofc.edu

76

Measuring Low-Level Concentrations of Trace Metals in Wet Deposition

Samples

Katie Blaydes1 and Lee Green2

Trace metals are released into the environment via natural and anthropogenic processes. Metals

such as Al, Mn, Fe, Cr, Ca2+ and K+ are indicative of soil contribution. The Earth’s crust is

enriched with many of these elements and Aeolian dusts can efficiently transport some crustal

elements and heavy metals. Non-crustal volatile metals, such as Cd, Zn, and Pb are characteristic

of fuel combustion and metal smelting. The Central Analytical Laboratory (CAL) has come up

with a method to measure low level concentrations in wet deposition samples via Inductively

Coupled Plasma Optical Emission Spectroscopy (ICP-OES).

1Central Analytical Laboratory, kblaydes@illinois.edu 2Central Analytical Laboratory, leegreen@illinois.edu

77

First Diagnosis of Allergenic Airborne Pollen and its Interaction with Atmospheric

Pollutants in the Mexico City Metropolitan Zone (MCMZ) and their Transport

and Dispersion in the Atmosphere

Ma Carmen Calderon E.1 , Rodolfo Sosa E

2, Benjamin Martínez l.

3, Cesar

Guerrero4, Juan Alcivar

5, Fernando Téllez U

6, Invonn Santiago L.

7, Ma Luisa

Alarcon J.8, Ma Carmen Torres B.

9, Pablo Sánchez A.

10 and Mónica Jaimes P.

11

Air pollution is one of the main characteristics of areas where human population density is very high; It plays

an important role in the health of the entire population. In addition to the atmospheric pollutants (gases and

particles) emitted by human activities, the atmosphere is the transport medium for a wide variety of biogenic particles. These include bioaerosols such as viruses, bacteria, fungi, plant fragments, pollen grains, their

allergenic proteins or small airborne particles containing pollen allergens.

Atmospheric pollutants have direct effects on pollen, modifying their biological and reproductive functions, causing a decrease in viability and germination; alteration of the physicochemical characteristics of the pollen

surface and its allergenic potential and adjuvant effect, increasing the potential risks to health. It has been

reported that pollutants such as O3, NO2, SO2 and atmospheric deposition (wet and dry) interact with allergenic pollen in the atmosphere aggravating asthma symptoms and particulate matter together with pollen

allergens play a very important role in increasing the allergic inflammatory response. Therefore, the

objective of this work was to perform a first diagnosis of airborne allergenic pollen from MCMZ, its interaction with atmospheric pollutants and their transport and dispersion in the atmosphere. Sampling of air

pollen grains was carried out at four city stations belonging to the Mexican Aerobiology Network (REMA)

during the period 2014 to 2016. Records of atmospheric pollutants and meteorological conditions, including wind fields, were analyzed for the same study period. The first spatial-temporal interpretation (diurnal and

seasonal cycle) was performed among all variables evaluated, their transportation through the atmosphere of

Mexico City and the risk to the health of the population were determined.

In this study, spatial and temporal variations in the air quality (RAMA Network) and chemical composition of

rain (REDA Network) in Mexico City between 2014 to 2016 were analyzed. Major ions (Na+, NH4+, K+,

Mg2+, Ca2+, SO42-, NO3

- and Cl-), pH, and electrical conductivity (EC) were analyzed weekly at 4 sampling stations located in the same region MCMZ.

Spatial distribution of wet atmospheric deposition shows that pH decreases throughout the study from north

to south in the MCMZ. In the stations located in a rural area, a strong correlation was found between NH4

+ and SO42-, NO3

-, and Cl-;

this is likely due to their origin in soil (i.e., fertilizer use).

The same concentration trend was observed for SO42- and NO3 in the MCMZ stations; this indicates that the

sources of acid rain precursors are upwind (i.e., to the north) of the study area.

Considering that external emission sources play a decisive role in driving acid rain within the MCMZ, it is

necessary to establish strategies for the emission reductions of acid rain precursors from upwind sources outside the MCMZ.

This shows the need to continue multidisciplinary studies as well as to expand the interaction among the

different available networks: REMA, REDA and RAMA 1Universidad Nacional Autonoma de Mexico (UNAM), mclce@atmosfera.unam.mx 2UNAM, rodsosa@unam.mx 3UNAM, ana.alarbenmaron@atmosfera.unam.mx 4UNAM, cgg@atmosfera.unam.mx 5UNAM, bio.alcivar@gmail.com 6UNAM, mclce@atmosfera.unam.mx 7UNAM, ivonnesantiagolopez@yahoo.com 8UNAM, alarcon@atmosfera.unam.mx 9UNAM, mcarmen@atmosfera.unam.mx 10UNAM, pasa@unam.mx 11UNAM, mjaimes@comunidad.unam.mx

78

Live Demo: Critical Loads Mapper Tool

Christopher Clark1, Amy Ramsdell2, Jen Phelan3, Jason Lynch4, Claire O'Dea5,

Anita Rose6, Bill Jackson7, Tamara Blett8 and Mike Bell9

The Critical Loads Mapper Tool is a EPA-USFS-NPS collaborative effort to enable decision

makers, researchers, and the public to easily access information on atmospheric deposition of

nitrogen and sulfur, critical loads, and their exceedances to better understand local and regional

vulnerability to atmospheric pollution. This interactive mapping tool displays nitrogen and sulfur

deposition levels through time for several air quality models, critical load levels for terrestrial and

aquatic ecosystems in the National Critical Loads Database, and the exceedance of deposition over the critical loads as an estimate of vulnerability to air pollution.

1EPA, clark.christopher@epa.gov 2Blue Raster LLC, aramsdell@blueraster.com 3RTI, jenphelan@rti.org 4EPA, Lynch.Jason@epa.gov 5USFS, cbodea@fs.fed.us 6USFS, anitarose@fs.fed.us 7USFS, bjackson02@fs.fed.us 8NPS, tamara_blett@nps.gov 9NPS, michael_d_bell@nps.gov

79

The Geospatial Monitoring of Air Pollution (GMAP) and its Role in Addressing

Critical Scientific Knowledge Gaps in Air Quality and Source Emissions

Justin Coughlin1, Marta Fuoco

2 and Scott Hamilton

3

The U.S. EPA Geospatial Mapping of Air Pollution (GMAP) project has been utilized to

determine stationary sources’ influence on surrounding air quality. The mobile GMAP platform

allows for air quality monitoring at ~1 sec resolution coupled with mobile 2D anemometer

measurements (vehicle speed corrected) and real-time GPS coordinates. Additionally, stationary

measurements are able to be conducted to determine source apportionment influences on monitor

readings. Currently, the GMAP system is equipped with a cavity ring-down spectroscopy

(CRDS) that is able to measure hydrogen sulfide (H2S) and methane (CH4) and a multi-pass UV

optical spectrometer that can measure benzene-toluene-ethylbenzene-xylene (BTEX), sulfur

dioxide (SO2), oxides of nitrogen (NOx), ozone (O3), formaldehyde, and styrene. During

stationary measurements, a 3D anemometer is also attached to provide 3D wind measurements

used to determine emissions flux estimates from ground level emission sources.

The GMAP platform has primarily been utilized to assess air quality impacts near facilities such

as landfills, wastewater treatment centers, oil and gas processes, and paper mills. With the

importance of ammonia (NH3) as a precursor in particulate matter (PM) formation and the

growing regulatory interest of decreasing NH3 emissions to limit PM pollution in the U.S., the

mobile geospatial measurement systems may be useful in both quantifying emission rates and

assessing plume size and variability, helping to fulfill critical knowledge gaps of NH3 emissions

and their role in regional PM concentrations. CRDS instruments are able to measure air

pollutants at a high degree of accuracy and precision with a relatively low residence time. NH3-

measuring instrumentation is being explored as a possible addition to the GMAP system.

1US EPA Region 5, coughlin.justin@epa.gov 2US EPA Region 5, fuoco.marta@epa.gov 3US EPA Region 5, hamilton.scott@epa.gov

80

Wet and Dry Deposition of Excess Chloride near a Hardrock Salt Mine

Jeremy Deitrich, Tom Butler*, Francoise Vermeylen and John Dennis

A preliminary study was undertaken to assess both wet and dry deposition of chloride in the vicinity of an

active salt mine in Lansing, NY. Multi-day sampling of 3 wet events and 3 dry events were undertaken using

triplicate NADP sampling buckets over a 5 station transect from 244 m to 600 m from the salt pile storage facilities at the mine. A 6th, control site was located 4100 m from the salt piles. Overall wet and dry

deposition rates were estimated for each site using a random effects model. Similar analyses were performed

on the conductivity of the wet samples, and dry samples with a standard addition of deionized water added to the dry sample buckets after collection. The transect was arranged north of the mine and deployments were

attempted when forecasts predicted that the transect area was going to be downwind of the mine, at least

some of the time. Summary results show the control site having an average daily wet deposition of 3.2 ±22.3 (s.e.) mg Cl-/m2

and a daily dry deposition of 3.1 ±22.5 mg Cl-/m2. Stations 1 through 4, located 250 to 550 m from the salt

piles, show a 40 to 75-fold increase in wet deposition and a 19 to 41-fold increase in the mean daily dry Cl- deposition, compared to the control site.

Combining wet + dry deposition on an annual basis, Cl- deposition was 25 to 48 times greater than the

control site for stations #1 through #4. Annual NaCl total deposition in kilograms per hectare were: Station #1, 904; #2, 837; #3, 725; #4, 470; and #5, 342, with a standard error of ~ ±20%. Our control location yields

an annual deposition rate of only 19 kg NaCl/ha. There is an excess of NaCl deposition of 61 metric tons/yr

for the 235 hectare area within a 500 m radius of the salt piles. Within a 1 km radius of the salt piles, the

excess NaCl deposition is 99 metric tons per year. These data suggest substantial excess chloride deposition

to the surrounding landscape, especially within ½ km of the salt piles. Visible damage to local vegetation and excess corrosion of metal nearby most likely from excess salt deposition, corroborates these findings.

*Corresponding author: tjb2@cornell.edu, 607 351 9926, 211 Rice Hall, Ithaca, NY 14853

81

Acidification and Climate Drive Increased Dissolved Organic Carbon in High

Elevation Lakes

Amanda Gavin1, Sarah J. Nelson

2, Amanda J. Klemmer

3, Ivan J. Fernandez

4,

Kristin E. Strock5 and William H. McDowell

6

Increasing concentrations of dissolved organic carbon (DOC) in the northeastern US have been

attributed to two potential mechanisms: recovery from acidification and changing climate. Due

to geology and landscape setting, Maine’s high elevation lakes (>600m) provide unique insight

into the response of surface water chemistry to declining acidic deposition and interannual

climate variability. Long-term geochemical response in 29 lakes was analyzed during 30 years of

change in sulfate (SO42-) deposition and climate. All 29 lakes exhibited positive trends in DOC

from 1986-2015, and 19 of 29 (65%) lakes had statistically significant increases in DOC

throughout the study period. These results illustrate a region-wide change from low DOC lakes

(<5 mg/L) to moderate DOC lakes (5-30 mg/L). Increasing DOC trends were more consistent

across high elevation lakes than in previous studies from lower elevation lakes in the northeastern

US. Net increases in DOC concentrations were correlated with net decreases in SO42-, and a

direct comparison of high elevation and low elevation lakes in Maine revealed greater extent of

acidification and larger increases in DOC concentrations in high elevation lakes. A linear mixed

effects models demonstrated that SO42- and climate variables describe most of variability in

DOC concentrations (r2 = .78). The strongest predictor of DOC concentration was an inverse

relationship with SO42- (p < 0.0001). Coefficient of variation (CV) of DOC in all lakes was

negatively correlated with air temperature, suggesting a homogenous DOC response to increasing

temperature. Due to SO42- concentrations trending towards pre-acidification levels and

projections of a warmer, wetter, and more variable climate, there is uncertainty for the future

trajectory of DOC trends in surface waters. Given the importance of DOC to lake

biogeochemistry, long-term monitoring of Maine’s high elevation lakes is increasingly important

to understand both recovery and response in surface water chemistry to a changing chemical and

physical environment in the decades ahead.

1University of Maine, amanda.gavin@maine.edu 2University of Maine Ecology and Environmental Sciences, sarah.j.nelson@maine.edu 3University of Maine Ecology and Environmental Sciences, amanda.klemmer@maine.edu 4University of Maine School of Forest Resources, ivanjf@maine.edu 5Dickinson College Environmental Science Department, strockk@dickinson.edu 6University of New Hampshire Department of Natural Resources and the Environment,

Bill.McDowell@unh.edu

82

Selecting Critical Loads of Atmospheric Deposition when the Response is

Continuous: A Case Study of Risk Assessment to Lichens

Linda Geiser1, Heather Root

2, and Peter Nelson

3

Empirical responses of terrestrial and aquatic organisms to the deposition of acidifying and

eutrophying air pollutants are often continuous. Whether the response metric be community

composition, growth rate, seedling survival, or something else, the absence of a discontinuity

signaling an obvious exceedance of a biological response threshold can make critical load

selection annoyingly subjective. How, by gum, does one evaluate harm—is even the smallest

measurable amount of change harmful? Here we share some ideas for assessing risk associated

with depositional loadings of 1.5, 2, 2.5, and 3 kg S and N ha-1 yr-1 to five lichen community

indices: sites scores calculated as the abundance weighted mean sensitivity of species present;

total species richness; forage lichen richness; cyanolichen richness; and sensitive species

richness. We use national-scale data to show how risk assessments can help managers select a

geographical-, climate-relevant critical load and explain the potential harm associated with its

exceedance.

1USDA Forest Service, Washington, DC 2Weber State University, Ogden, UT 3University of Maine, Ft. Kent, ME

83

A Pilot Study of the Radiello Passive Ammonia Samplers at Three Canadian

(CAPMoN) Sites with Comparisons to Continuous Measurements and Satellite

Retrievals

Edward Hare1, Robert Vet

2, Jason O'Brien

3, Richard Tanabe

4, Mark Shephard

5,

Shailesh Kharol6 and Christopher M.B. Lehmann

7

The Canadian Air and Precipitation Monitoring Network (CAPMoN) has increased its efforts in

monitoring of ammonia by establishing three sites in central and eastern Canada to test the

effectiveness of the AMoN Radiello passive ammonia samplers for potential inclusion into the

mainstream CAPMoN suite of measurements. Three evaluation sites, Kejimkujik, Nova Scotia

and two Ontario sites at Bonner Lake and Longwoods all began sampling in October 2013. The

data presented in this poster examines the annual cycles, the application of a temperature

adjustment to account for the extended temperature range of measurements and also establishing

a method detection limit (MDL). In addition, some of the challenges encountered with the

application of travel and lab blanks to the data records will also be examined and presented. In

March 2017 the two Ontario sites were moved to Saskatchewan (Flat Valley and Pinehouse

Lake) where the Radiello samplers are collocated with continuous ammonia monitoring

instruments. This move was facilitated to extend the study by adding the comparison of these bi-

weekly aggregate values to the continuous measurements using a modified Thermo 42i-TL

instrument and a Picarro G2103. The two week integrated values from the Radiello are

compared with an equivalent bi-weekly integrated record from the continuous measurements. In

turn, these records are compared to Cross-track Infrared Sounder (CrIS) satellite ammonia

retrievals both as the integrated values and as discrete point-to-point comparisons during each

satellite overpass. Preliminary results will be presented.

1Environment and Climate Change Canada (ECCC), ed.hare@canada.ca 2Environment and Climate Change Canada (ECCC), robert.vet@canada.ca 3Environment and Climate Change Canada (ECCC), jason.o'brien2@canada.ca 4Environment and Climate Change Canada (ECCC), richard.tanabe@canada.ca 5Environment and Climate Change Canada (ECCC), mark.shephard@canada.ca 6Environment and Climate Change Canada (ECCC), shailesh.kharol@canada.ca 7Univ. Illinois, Prairie Research Institute, ISWS, clehmann@illinois.edu

84

Glyphosate: Understanding its Atmospheric Transport and Fate

Christopher Lehmann1, David A. Gay

2, John W. Scott

3 and Wei Zheng

4

Glyphosate is a widely used agricultural chemical in the United States. It's an environmental

contaminant of concern as a suspected carcinogen, although an evaluation of its health effects is

ongoing. There is a need to better understand its transport and fate in the environment,

particularly in sensitive ecosystems. Glyphosate is non-volatile and sorbs to soil particles.

Studies have detected it in air and rainwater samples, suggesting that its transport and fate in the

atmosphere is linked to airborne particulate matter. The Illinois State Water Survey (ISWS) and

the Illinois Sustainable Technology Center (ISTC) have performed limited studies to assess the

transport of glyphosate in the atmosphere.

The National Atmospheric Deposition Program (NADP) within ISWS collects rainwater and

snowmelt samples at more than 300 locations across North America. Preliminary work performed

at ISTC has demonstrated that glyphosate and several of its environmental decomposition

products can be readily measured by liquid chromatography tandem mass spectrometry (LCMS)

down to 60 ng/L.

1NADP/CAL; University of Illinois, clehmann@illinois.edu 2NADP; University of Illinois, dgay@illinois.edu 3Prairie Research Institute; Univ. Illinois, zhewang@illinois.edu 4Prairie Research Institute; Univ. Illinois, weizheng@illinois.edu

85

Evaluation of Ammonia Air-Surface Exchange at the Field Scale: Improvement of

Soil and Stomatal Emission Potential Parameterizations

Nebila Lichiheb1, LaToya Myles

2, Erwan Personne

3, Mark Heuer

4 and Michael

Buban5

Intensive agriculture typically uses nitrogen-based fertilizers to increase yields for sustaining a

growing human population. Agriculture is the main source of atmospheric emissions of ammonia

(NH3), a precursor to particulate matter in the atmosphere. The impact of NH3 emissions on air

quality is of concern in the U.S. due to adverse effects on human health, and terrestrial and

aquatic ecosystems. With reductions in nitrogen oxide emissions due to legislation

implementation, the importance to NH3 for particulate matter formation and atmospheric

deposition of reactive nitrogen has increased. Emissions of NH3 from fertilized cropland occur as

soon as fertilizer is applied on the farmed surface and emission can last from a few days to

several weeks, depending on the properties of the specific fertilizer, plant properties,

pedoclimatic conditions, environmental conditions, and agricultural practices. The complex

interactions between agronomic and environmental conditions make necessary the use of

modeling to study the NH3 volatilization.

In this study, we implemented in the SURFATM-NH3 model, which simulates the bi-directional

exchanges of NH3 between the biogenic surface and the atmosphere, a new parameterization of

the stomatal and ground layer emission potentials (Γs and Γg). This operational parameterization

enables a dynamic modelling of Γs and Γg by taking into account the N status of the plant which

includes the N input and the atmospheric N deposition.

This new parameterization was evaluated with a dataset comprising NH3 fluxes measured using

the flux-gradient (FG) and relaxed eddy accumulation (REA) methods in a corn canopy fertilized

with UAN and urease inhibitor NBPT over a period of approximately 3 months at the Energy

Farm at the University of Illinois at Urbana‐Champaign, IL, USA. The results showed that the

SURFATM- NH3 model satisfactorily simulates the NH3 fluxes by implementing the

parameterization of Γs and Γg and by taking into account the effect of the urease inhibitor. The

latter need to be more closely examined because it had a considerable effect on the rate and

extent of NH3volatilization.

1NOAA/ATDD, nebila.lichiheb@noaa.gov 2NOAA/ATDD, latoya.myles@noaa.gov 3INRA-AgroParisTech, erwan.personne@agroparistech.fr 4NOAA/ATDD/ORAU, mark.heuer@noaa.gov 5NOAA/ATDD/ORAU, michael.buban@noaa.gov

86

N Deposition Effects on Hermes Copper Butterfly (Lycaena hermes) Habitat in

Southern California

Liberty Malter1, George Vourlitis

2, Alison Anderson

3 and Tracey Brown

4

Atmospheric nitrogen (N) deposition has become a global concern over the past few decades as

population sizes have increased. San Diego County, CA, USA, with a high population density,

Mediterranean-type climate, and high biodiversity, is an ideal site for an extensive N deposition

study. Chronic anthropogenic N deposition is one of the main contributing factors to affect plant

species diversity (Vourlitis and Pasquini 2009) and invasive species encroachment (Minnich and

Dezzani 1998). It is also the location of the rare endemic Hermes copper butterfly (Lycaena

hermes), which has received minimal research and remains a mystery to many ecologists. We

hypothesized that N deposition will impact Hermes abundance; however, there is limited research

on the effects of N deposition on butterfly habitat. Thus, this study aims to determine the effect of

increased N on the alterations to plant-insect interactions. These effects are being measured at

five sites throughout San Diego County in current or historical Hermes copper habitat. N

deposition collectors have been placed under the canopy of spiny redberry shrubs (Rhamnus

crocea) to accumulate N throughfall at each site. Soil and redberry stem fragments are being used

to analyze total N and Carbon (C), water potential, and shrub growth throughout the course of

this study. Despite the preliminary nature of our results, we show a number of trends between

data groups, such as large differences in soil and tissue N and C between the study sites,

suggesting differences in atmospheric N inputs. These variations in soil N availability lead to

variations in leaf tissue chemistry, which can ultimately impact the performance of the Hermes

copper larvae. Our current data demonstrate some clear trends, but whether these trends remain

consistent and interpretable remains to be seen. We anticipate this research will increase our

understanding of spatial variation patterns of N deposition in southern California and how that N

input might affect the rare Hermes copper butterfly and its host plant, Rhamnus crocea.

Furthermore, these data are important because they might help us understand why Hermes is in

decline and which sites should be prioritized for management.

1California State University San Marcos, isbel007@cougars.csusm.edu 2California State University San Marcos, georgev@csusm.edu 3United States Fish and Wildlife Service, alison_anderson@fws.gov 4California State University San Marcos, traceyb@csusm.edu

87

Evaluating Variation in Sources of Atmospheric Nitrogen Deposition in the Rocky

Mountains using d15

N−NO3− and d

15N−NH4

+

Leora Nanus1, Christopher M.B. Lehmann

2 and M. Alisa Mast

3

Spatial and temporal variation in sources of nitrogen (N) deposition to high-elevation ecosystems

in the Rocky Mountains were evaluated using N isotope data for water years 1995-2016. This

unique dataset links N in wet deposition and snowpack to emissions sources, and improves

understanding of the impacts of anthropogenic activities and environmental policies that mitigate

effects of accelerated N cycling. d15N−NO3− at 50 US Geological Survey Rocky Mountain

Snowpack sites ranged from −3.3 ‰ to +6.5 ‰, with a mean value of +1.4 ‰. At 15 National

Atmospheric Deposition Program (NADP)/National Trends Network wet deposition sites,

summer d15N−NO3− is significantly lower ranging from −7.6 ‰ to −1.3 ‰ while winter

d15N−NO3− ranges from −2.6 ‰ to +5.5 ‰, with a mean value of +0.7 ‰ during the cool season.

Winter NADP wet deposition d15N−NO3− is lower than snowpack, possibly due to the influence

of dry deposition in the snowpack. Spatial trends in wet deposition are similar to Snowpack, with

higher NO3− concentrations and d15N−NO3

− in the Southern Rockies located near larger

anthropogenic N emission sources compared to the Northern Rockies. Wet deposition

d15N−NH4+ ranged from −10 ‰ to 0 ‰, with no observed spatial pattern. However, the lowest

d15N−NH4+(−9 ‰), and the highest NH4

+ concentration (35 meq/L) were observed at a Utah site

dominated by local agricultural activities, whereas the higher d15N−NH4+ observed in Colorado

and Wyoming are likely due to mixed sources, including fossil fuel combustion. These

findings show spatial and seasonal variation in N isotope data that reflect differences in sources

of anthropogenic N deposition to high-elevation ecosystems and have important implications for

environmental policy.

1San Francisco State University, lnanus@sfsu.edu 2NADP, Illinois State Water Survey, clehmann@illinois.edu 3US Geological Survey, mamast@usgs.gov

88

An Air Quality Portal to Support the Use of Critical Loads of Atmospheric

Deposition in National Forest and Grassland Planning

Claire O’Dea1, Linda Geiser

2, Rich Pouyat

3, Anita Rose

4, and Linda Pardo

5

Forest Plans provide the basis for management decisions made on national forests and grasslands

of the United States. The USDA Forest Service 2012 Planning Rule requires national forest and

grassland managers to consider air quality when developing plan components and to treat air

resources similar to soil and water resources. This provides a unique opportunity to standardize

the way national forests view and manage air quality as a forest resource. By creating an easy-to-

use resource to guide managers in considering and treating air quality, we can ensure a nationally

consistent methodology which incorporates the best available science and data and eases the

burden on the managers. The Air Quality Portal ensures that managers understand the concept of

critical loads of air pollution, allowing for appropriate incorporation of critical loads/exposures

and target loads/exposures into Forest Plan revisions to meet the intent of the 2012 Planning

Rule. The Portal hosts the following documents:

Decision tree guiding a nationally standardized air quality assessment process to

determine exceedances of critical loads of air pollution

Decision trees guiding monitoring and management decisions based on the results of

the air quality assessment

Detailed protocols/instructions for following assessment process

Spatial data available for download (and/or potentially for web viewing)

Sample specialist report(s)

Briefing papers and other communications tools

Training tools

The Air Quality Portal, accessible from https://www.srs.fs.usda.gov/airqualityportal/, will be

demonstrated live by US Forest Service staff during the poster session of the NADP meeting.

1USDA Forest Service, cbodea@fs.fed.us 2USDA Forest Service, lgeiser@fs.fed.us 3USDA Forest Service, rpouyat@fs.fed.us 4USDA Forest Service, anitarose@fs.fed.us 5USDA Forest Service, lpardo@fs.fed.us

89

HANDS-ON CRITICAL LOADS TOOL DEMO: N-CLAS

Effects of Climate, Site and Soil Characteristics on Critical Loads and Exceedance

in Forests in the Northeastern U.S.

Linda Pardo1, Jason A. Coombs

2, Molly Robin-Abbott

3, Jennifer Pontius

4 and

Claire B. O’Dea5

Assessing the impacts of the multiple threats impacting ecosystem health and sustainability over

the long term, in particular climate change and nitrogen (N) deposition, remains a critical

challenge for resources managers and policy makers. To facilitate such assessments, we

developed a GIS-based tool, Nitrogen Critical Loads Assessment by Site (N-CLAS), which

calculates critical loads and exceedances for N deposition to forests in the northeastern US. It

provides high resolution outputs (maps, graphs, and tables) for multiple areas and accounts for

the influence of site, climate, and topographic conditions on 23 key tree species in the region. N-

CLAS evaluates the impact of multiple stressors (N deposition and climate change)

simultaneously for species of management concern on forest lands in the Northeast and Upper

Midwest. In addition to calculating species-specific critical loads, N-CLAS is designed to take

into account the impact of site abiotic factors on the response of trees to N deposition. The

abiotic modifying factors include, precipitation, temperature (e.g., January T, July T, May-

September T), and soil characteristics. This tool is designed N-CLAS facilitates assessment of

risk to forest ecosystems for resource managers and policy makers.

In this hands-on demo session, we will demonstrate how to use the tool, the types of outputs it

produces, and the ways that it can be utilized to assess extent and magnitude of risk to forest ecosystems and to evaluate the susceptibility of individual tree species.

1USDA Forest Service, lpardo@fs.fed.us 2USDA Forest Service, jcoombs@cns.umass.edu 3USDA Forest Service, mjrobina@gmail.com 4UVM/USDA Forest Service, japontiu@uvm.edu 5USDA Forest Service, cbodea@fs.fed.us

90

Effects of Climate, Site and Soil Characteristics on Critical Loads and Exceedance

in Forests in the Northeastern U.S.

Linda Pardo1, Molly Robin-Abbott

2, Claire O'Dea

3, Jennifer Pontius

4 and Jason

Coombs5

Assessing the impacts of the multiple threats impacting ecosystem health and sustainability over

the long term, in particular climate change and nitrogen (N) deposition, remains a critical

challenge for resources managers and policy makers. To facilitate such assessments, we used a

GIS-based tool, Nitrogen Critical Loads Assessment by Site (N-CLAS), to evaluate the impact of

multiple stressors (N deposition and climate change) simultaneously for species of management

concern on forest lands in the Northeast and Upper Midwest. In addition to calculating species-

specific critical loads, N-CLAS is designed to take into account the impact of site abiotic factors

on the response of trees to N deposition. The abiotic modifying factors include, precipitation,

temperature (e.g., January T, July T, May-September T), and soil characteristics. We conducted

our analysis for the full region and at the Ecoregion levels 2 and 3. Application of N-CLAS

across the northeastern U.S. allows us to evaluate which areas and tree species are most

susceptible to impacts from N deposition. In this analysis, we determined the critical load and

exceedance for individual tree species and all the species present. We also evaluated the extent

and magnitude of the CL exceedance and how that would change under future deposition

scenarios. N-CLAS facilitates analysis of the extent of the area impacted by N deposition which

provides resource managers with a simple way to incorporate the current state-of-the-science

knowledge into their planning and management decisions.

1US Forest Service, lpardo@fs.fed.us 2US Forest Service, mjrobina@gmail.com 3US Forest Service, cbodea@fs.fed.us 4UVM/US Forest Service, japontiu@uvm.edu 5US Forest Service, jcoombs@cns.umass.edu

91

Atmospheric Elemental Carbon Deposition to Oak Trees and Litterfall Flux to

Soil in an Urban Area

Jenna Rindy1, Alexandra G. Ponette-González

2, Tate E. Barrett

3 and Brett W.

Luce4

Elemental Carbon (EC), a product of incomplete combustion of fossil fuels and biomass,

contributes to climate warming and poor air quality. In urban areas, diesel fuel trucks are the

main source of EC emissions from mobile sources. After emission, EC is deposited to receptor

surfaces via two main pathways: precipitation (wet deposition) and directly as particles (dry

deposition). Urban trees may play an important role in removing EC from the atmosphere by

intercepting and delivering it directly to the soil. The goal of this research is to quantify the

magnitude of EC retention on leaf surfaces (leaf EC) and EC fluxes to soil via leaf litterfall in the

City of Denton, Texas. Denton is a rapidly growing urban area north of the Dallas-Fort Worth

metropolitan Area. We are using a foliar extraction technique to determine EC retention on leaf

surfaces. Foliar samples are being collected monthly, from April to November, from co-

located Quercus stellata (post oak, n = 10) and Quercus virginiana (live oak, n = 10) trees.

Samples are rinsed with water and chloroform in a two-step process to determine surface-

deposited EC and EC retained in leaf waxes. A Sunset EC/OC carbon analyzer will be utilized to

analyze EC content of extracts filtered onto quartz-fiber filters. For one year, leaf litter is being

collected bi-weekly under 35 trees (20 post oak, 15 live oak), and oven dried to determine dry

weight. EC retained by tree canopies will be calculated by multiplying leaf EC by canopy leaf

area index, while EC flux to soil will be estimated by multiplying in-wax EC by leaf litterfall

mass. Here, preliminary results of EC retention on leaf surfaces, as well as EC flux to soil for

spring and summer 2017 are presented. Results of this study will assess urban tree’s ability to

filter air pollution and mitigate climate change.

1University of North Texas, jenna.rindy@unt.edu 2University of North Texas, alexandra.ponette@unt.edu 3University of North Texas, tate.barrett@unt.edu 4University of North Texas, BrettLuce@my.unt.edu

92

CASTNET Ozone Monitoring Program

Christopher Rogers1, Timothy Sharac

2, Melissa Puchalski

3, Marcus Stewart

4,

Kevin Mishoe5 and Kemp Howell

6

The Clean Air Status and Trends Network (CASTNET) is a long-term monitoring network

designed to measure acidic pollutants and ambient ozone (O3) concentrations in rural areas in the

United States and Canada. CASTNET is managed collaboratively by the Environmental

Protection Agency – Clean Air Markets Division (EPA), the National Park Service – Air

Resources Division (NPS), and the Bureau of Land Management – Wyoming State Office (BLM-

WSO). In addition to EPA, NPS, and BLM-WSO, numerous other participants provide site

operator support and grant land access including North American tribes, other federal agencies,

States, private land owners, and universities.

Eighty-two CASTNET sites report hourly O3 concentrations. The data provide accountability for

EPA’s regional Nox emission reduction programs (i.e. Nox SIP Call, Cross State Air Pollution

Rule, and Cross State Air Pollution Rule Update) and exposure effects on vegetation. The

National Park Service uses CASTNET O3 data to develop strategies for improving visibility and

protecting resources within park boundaries. Additionally, eighty of the O3 monitors at

CASTNET sites meet the requirements of Title 40 of the Code of Federal Regulations (CFR) Part

58 and are used to determine compliance with the O3National Ambient Air Quality Standard

(NAAQS). Populations located in areas that exceed the primary NAAQS are more susceptible to

adverse health effects. CASTNET provides a unique dataset to rural populations where state-

operated O3 monitors are not required.

Each CASTNET monitor measures ambient O3 concentrations for the entire year. CASTNET

O3 data are submitted to the AIRNow Tech website for near-real time reporting

(www.airnowtech.org) and to EPA’s Air Quality System (AQS) database

(https://aqs.epa.gov/aqs). Annual performance evaluations (PE) and results from the National

Performance Audit Program (NPAP) are also submitted to AQS routinely.

Preliminary 2014-2016 3-year average of the fourth highest daily maximum rolling 8-hour

averages calculated using the 2015 ozone NAAQS indicate that four CASTNET sites exceed the

70 ppb O3 NAAQS including Joshua Tree National Park, CA; Sequoia National Park, CA;

Yosemite National Park, CA; and Washington Crossing, NJ.

Ozone data and additional information about the CASTNET monitoring program can be found on

the CASTNET webpage at https://www.epa.gov/castnet.

1Amec Foster Wheeler, christopher.rogers@amecfw.com 2USEPA, Sharac.Timothy@epa.gov 3USEPA, Puchalski.Melissa@epa.gov 4Amec Foster Wheeler, Marcus.Stewart@amecfw.com 5Amec Foster Wheeler, Kevin.Mishoe@amecfw.com 6Amec Foster Wheeler, Kemp.Howell@amecfw.com

93

Characterization of Reduced Nitrogen at IMPROVE and CSN Monitoring Sites in

the Southeastern United States

Christopher Rogers1, John Walker

2, Rich Scheffe

3, Kevin Mishoe

4, Doris Chen

5,

Katherine Barry6, Melissa Puchalski

7, Bret Schichtel

8 and Joann Rice

9

The Interagency Monitoring of Protected Visual Environments (IMPROVE) and Chemical

Speciation (CSN) networks have provided two decades of routine particulate matter (PM)

speciation data that support regional haze and PM NAAQS programs. As shown by the NADP

wet deposition record over the same period, the chemical composition of the ambient atmosphere

has changed markedly from one dominated by nitrate, sulfate, and carbonaceous aerosols, and

their associated precursor gases to an atmospheric mixture that includes a significant amount of

reduced inorganic nitrogen – particulate ammonium (NH4+) and its precursor gas, ammonia

(NH3). The magnitude of this change is reflected by a nationwide shift in the atmospheric

composition from one dominated by inorganic oxidized compounds, to one where reduced

inorganic nitrogen species (NHx = NH3 + NH4+) now have similar or greater contributions to the

total nitrogen budget.

To address this change, it becomes necessary to characterize reduced nitrogen emission sources

and atmospheric composition. Previous studies conducted primarily in the western United States

have examined the possibility of using acid-impregnated filters in the IMPROVE system to

measure NHx. Results were considered successful leading to a current study using acid-

impregnated filters in both the IMPROVE and CSN systems to conduct similar measurements in the southeastern United States.

The study is occurring from late May through late November 2017 at Duke Forest, NC (near

Research Triangle Park) and Gainesville, FL. Both sites are running CSN, IMPROVE, and URG

annular denuder systems as the reference method to measure NHx. In addition, both sites include

NH4+ and NH3 measurements from the CASTNET filter pack and NADP/AMoN, respectively.

The Duke Forest site also has a Monitor for Aerosols and Gases in Ambient Air (MARGA)

collecting hourly measurements of NH3 and NH4+. Here, results from the Duke Forest and

Gainesville sites are compared to determine the feasibility of adding an acid-impregnated filter to capture NHx at a subset of the IMPROVE and CSN long-term measurement stations.

1Amec Foster Wheeler, christopher.rogers@amecfw.com 2USEPA, Office of Research and Development, Walker.Johnt@epa.gov 3USEPA, Office of Air Quality Planning and Standards, Scheffe.Rich@epa.gov 4Amec Foster Wheeler, Kevin.Mishoe@amecfw.com 5USEPA, Office of Research and Development, Chen.Xi@epa.gov 6Amec Foster Wheeler, Katherine.Barry@amecfw.com 7USEPA, Clean Air Markets Division, Puchalski.Melissa@epa.gov 8NPS, Cooperative Institute for Research in the Atmosphere, Colorado State University,

Bret.Schichtel@colostate.edu 9USEPA, Office of Air Quality Planning and Standards, Rice.Joann@epa.gov

94

The Atmospheric Chemistry and Canopy Exchange Simulation System

for Ammonia (ACCESS-NH3): Formulation and Application to a Corn

Canopy

Rick Saylor1, LaToya Myles

2, Nebila Lichiheb

3, Mark Heuer

4, Andrew

Nelson5, Sotiria Koloutsou-Vakakis

6and Mark Rood

7

As nitrogen oxide and sulfur dioxide emissions decrease in the U. S. as a result of implemented

air quality regulations, agricultural emissions of ammonia (NH3) are being recognized as playing

an increasingly important role in fine particle (PM2.5) formation. If regulations on agricultural

emissions are implemented in the future, it will be necessary to have reliable models of NH3 bi-

directional exchange over a variety of crop types to help formulate effective control or mitigation

strategies. The Atmospheric Chemistry and Canopy Exchange Simulation System for Ammonia

(ACCESS-NH3) is a multilayer, single column model that simulates the bi-directional transport

and exchange of ammonia throughout the soil-plant-atmosphere continuum. In this presentation,

the ACCESS-NH3 modeling system is described and results from its application to a corn (Zea

mays) canopy are presented. NH3 concentration and flux measurements, along with

micrometeorological and environmental observations, were made within and above a Zea mays

canopy at the University of Illinois Energy Biosciences Institute Energy Farm in Urbana, IL,

during the entire growing season of 2014. ACCESS-NH3 has been applied to the data obtained

during this field experiment to evaluate the model and to assess how NH3 interacts with the Zea

mays canopy and how these interactions vary over the growing season and as a function of environmental conditions. Results from the evaluations and simulations will be presented.

1NOAA/ARL/ATDD, rick.saylor@noaa.gov 2NOAA/ARL/ATDD, latoya.myles@noaa.gov 3ORAU, nebila.lichiheb@noaa.gov 4NOAA/ARL/ATDD, mark.heuer@noaa.gov 5University of Illinois at Urbana-Champaign, andrew.j.nelson1@gmail.com 6University of Illinois at Urbana-Champaign, sotiriak@illinois.edu 7University of Illinois at Urbana-Champaign, mrood@illinois.edu

95

Long-term Trends in Atmospheric Sulfur and Nitrogen Species across the United

States: 30 years of Clean Air Status Network (CASTNET) Operations

David Schmeltz1, Melissa Puchalski

2, Gary Lear

3, Greg Beachley

4, Kemp Howell

5,

Taylor Macy6, Chris Rogers

7, Tim Sharac

8 and Marcus Stewart

9

The Clean Air Status and Trends Network (CASTNET) and the National Atmospheric

Deposition Program (NADP) offer a robust capability to investigate long-term trends in

atmospheric concentrations and deposition of sulfur and nitrogen species in rural areas of the

U.S. The U.S. EPA, National Park Service, and the Bureau of Land Management (Wyoming

State Office) manage the CASTNET program and network operations at 90+ sites located

throughout the contiguous US, Alaska, and Canada. For nearly three decades, CASTNET has

produced data of proven quality following consistent methods required for long-term trends

analysis. Observational data from CASTNET (and NADP) are used commonly to assess the

effectiveness of emission control policies, to evaluate and develop air quality models, and are

important inputs to critical load assessments and ecosystem studies. CASTNET is recognized as

a dynamic and resilient program that has evolved to respond to changing agency objectives and

emerging issues while still maintaining a consistent set of measurements (SO2, HNO3, SO4, NO3,

NH4, base cations, CL, and O3) over time in the face of static or declining federal budgets.

CASTNET complements measurements from co-located or nearby air quality monitoring

network sites (i.e. NCore, Chemical Speciation Network, Interagency Monitoring of Protected

Visual Environments). Further, the CASTNET platform has facilitated new deposition and effects

research and methods development geared toward reducing uncertainties in the nitrogen budget.

Here we present results from CASTNET, featuring regional long-term trends (1990-2016) in

atmospheric concentrations and estimates of dry deposition of key sulfur and nitrogen species.

We also look at how the network has adapted to advance deposition research, reduce spatial gaps

in remote areas, and build or expand upon existing partnerships to meet the evolving needs of the

policy and scientific communities. Finally, we discuss the challenges the network will face in the

next 5-years and plans for minimizing the impacts of those challenges.

1EPA, schmeltz.david@epa.gov 2EPA, puchalski.melissa@epa.gov 3EPA, lear.gary@epa.gov 4EPA, beachley.gregory@epa.gov 5Amec Foster Wheeler, Inc., kemp.howell@amecfw.com 6EPA, macy.taylor@epa.gov 7Amec Foster Wheeler, Inc., christopher.rogers@amecfw.com 8EPA, sharac.timothy@epa.gov 9Amec Foster Wheeler, Inc., marcus.stewart@amecfc.com

96

Mobile Measurements of Atmospheric Ammonia in Northeastern

Colorado

Yixing Shao1, Jeffrey L. Collett, Jr.

2 and Katherine B. Benedict

3

The spatial and temporal variability of ammonia is not well characterized in regions like

northeastern Colorado where there are large agricultural sources adjacent to urban and remote

areas. Northeastern Colorado is of interest since it is home to Rocky Mountain National Park

(RMNP), a protected area experiencing the effects of increased nitrogen deposition. To protect

the park from increasing nitrogen deposition it is crucial to understand the degree to which the

urban and agricultural sources are impacting RMNP, as well as how meteorological conditions

are influencing the ammonia concentrations and nitrogen deposition in the park. Mobile

measurements of ammonia were made in June 2016 to examine the spatial variability of ammonia

at high-time resolution. These data, together with modeling results from the Hybrid Single

Particle Lagrangian Integrated Trajectory Model (HYSPLIT), will be used to investigate the

transport of ammonia across the region. From previous observations it is unclear whether distinct

plumes of ammonia are being transported over large distances or whether regional ammonia

concentrations are relatively homogeneous. The combination of these measurements and

modeling results will provide a clearer picture of how ammonia-rich air parcels in the eastern plains of Colorado are transported and contribute to nitrogen deposition in the park.

1Colorado State University, yxshao@engr.colostate.edu 2Colorado State University, Jeffrey.Collett@colostate.edu 3Colorado State University, Katherine.Benedict@colostate.edu

97

Deposition of Atmospheric Mercury to the Lulin Atmospheric Background Station

(LABS) in Taiwan in 2009-2016

Guey-Rong Sheu1, Nguyen Ly Sy Phu

2, Da-Wei Lin

3, Leiming Zhang

4 and Neng-

Huei Lin5

Although East Asia is the major anthropogenic mercury (Hg) emission source region, studies

concerning atmospheric Hg deposition in its downwind region are still limited. Taiwan is

considered downwind of the East Asian continent in fall, winter and spring because of regional

monsoon activity. Monitoring of various atmospheric Hg species, including gaseous elemental

Hg (GEM), gaseous oxidized Hg (GOM) and particle-bound Hg (PBM), began since April 2006,

whereas collection of weekly rainwater samples for total Hg analyses began since early 2009, at

the Lulin Atmospheric Background Station (LABS; 120.87ºE, 23.47ºN, 2862 m a.s.l.), a tropical

mountain-top site in central Taiwan. Here we reported the wet and dry deposition of atmospheric

Hg to the LABS between 2009 and 2016. Dry deposition of speciated Hg was estimated using

bidirectional air-surface resistance model. Amounts of annual rainfall ranged from 2160 to 4991

mm and the volume-weighted mean concentrations of rainwater Hg ranged from 5.04 to 13.08 ng

L-1. Annual wet Hg deposition fluxes ranged between 10.89 and 46.05 µg m-2, with a grand

average of 27.3 µg m-2 yr-1. Wet Hg deposition fluxes were higher in summer as a result of higher

rainfall and rainwater Hg concentrations. Weekly wet deposition fluxes and rain depths were

highly correlated (R2 = 0.654, p < 0.01). As there is no anthropogenic Hg emission source around

the LABS, the high summertime rainwater Hg concentration hints at the importance of

Hg0 oxidation and/or scavenging of upper-altitude Hg(II) by deep convection. Annual dry

deposition fluxes ranged from 51.79 to 70.15 µg m-2, with a grand average of 60.8 µg m-2 yr-1. On

average, the annual dry deposition flux was 2.2 times that of wet flux. Nighttime GOM dry

deposition flux (8.09±1.96 µg m-2 yr-1) was higher than that of daytime (5.21±1.58 µg m-2 yr-1)

because of higher GOM concentration and wind speed at night. Due to the high percentage of

forest canopy coverage around the LABS, average annual GEM dry deposition flux (47.2 µg m-2)

was significantly higher than GOM (13.31 µg m-2) and PBM (0.21 µg m-2). Results of this

research indicate that wet and dry Hg deposition fluxes to the tropical mountain site are

significantly higher than values reported from sites in temperate region.

1National Central University, grsheu@atm.ncu.edu.tw 2National Central University 3National Central University 4Environment and Climate Change Canada 5National Central University

98

AMoN Site Characterization Study: Phase I Field Measurements

John Walker1, Kevin Mishoe

2, Christopher Rogers

3, Zhiyong Wu

4, Melissa

Puchalski5, Donna Schwede

6, Kim Hutchison

7, Wayne Robarge

8 and Ralph

Baumgardner9

Reduced inorganic nitrogen (NH3 + NH4+) is an increasingly important contributor to the total

nitrogen deposition budget, yet the bi-directional nature of NH3 air-surface exchange makes

incorporation of NH3 measurements into dry deposition schemes in field-scale and regional

chemical transport models (i.e. CMAQ) difficult. The purpose of this study is to develop a

methodology for providing NADP with modeled NH3 fluxes using bi-weekly AMoN

concentrations. NH3 fluxes derived from site specific NH3 measurements (AMoN) and surface

parameterizations (i.e., compensation points) will provide “best” estimates of NH3 deposition for

developing ecosystem specific deposition budgets, assessing sub-grid variability of fluxes within

CMAQ, and characterizing the impact of bias correcting CMAQ NH3 concentrations on

NH3 fluxes. This effort will therefore improve the total nitrogen deposition estimates provided

by TDEP, which does not currently use the AMoN NH3 concentrations for deposition estimates.

The first phase of the project will focus on measurements while the 2nd phase will focus on

evaluation of the bi-directional air-surface exchange model. During Phase I, a database of soil

and vegetation chemistry, micrometeorology, and surface physical characteristics will be

developed for 3 pilot sites: Chiricahua National Monument, AZ (desert); Bondville, IL

(agricultural); and Duke Forest, NC (hardwood forest). These sites were selected based on

available data (AMoN, CASTNET, and NADP/NTN), and differences in land-use type,

vegetation and soil types, and average ambient NH3 concentrations. Soil, live vegetation, and

litter will be collected and analyzed for NH4+ and pH to develop seasonal estimates of surface

NH3 emission potentials (Г) from which compensation points will be derived. Biogeochemistry

will be combined with on-site meteorology and surface characteristics will be used to calculate

net and component fluxes (i.e., foliage versus ground) using a 2-layer bi-directional flux model.

Measurements will be used to assess model sensitivities to biogeochemical and meteorological

inputs to develop a model suitable for implementation across the entire AMoN network.

Field measurements began in the summer of 2017 and will continue through spring 2018. Here

we describe the field and laboratory measurement methods that have been designed to capture a

robust biogeochemical dataset for the 3 AMoN pilot sites. Aspects of model development and

evaluation will also be discussed. 1US Environmental Protection Agency, walker.johnt@epa.gov 2Amec Foster Wheeler, kevin.mishoe@amecfw.com 3Amec Foster Wheeler, christopher.rogers@amecfw.com 4US Environmental Protection Agency, wu.zhiyong@epa.gov 5US Environmental Protection Agency, puchalski.melissa@epa.gov 6US Environmental Protection Agency, schwede.donna@epa.gov 7North Carolina State University, knhutchi@ncsu.edu 8North Carolina State University, wayne_robarge@ncsu.edu 9US Environmental Protection Agency, baumgardner.ralph@epa.gov

99

Testing Coastal Lichen and Moss Species as a Bioindicator of Atmospheric Total

Mercury and Monomethylmercury in Santa Cruz County, CA

Belle Zheng1, Wendy Lin

2, Peter Weiss-Penzias

3, Ken Kellman

4, Alfred

Freeberg5 and Brian Young

6

Lichen are unique terrestrial organisms that form stable mutualistic associations between fungi,

algae and cyanobacteria.. They have also been used as indicators of healthy air as they are able to

accumulate airborne pollutants such as heavy metals like mercury in their thalli (vegetative

tissue). A previous study done in the Canadian High Arctic found that lichen had median

monomethylmercury (MMHg) and median total mercury (THg) concentrations that were two

orders higher of magnitude than the soils underlying them. Intrigued by these data, we decided to

test the concentrations of MMHg and THg in lichen and moss in Santa Cruz, CA. The main

purpose of the study is to find out whether lichens and mosses can be used as bioindicators of

environmental mercury, especially the effects of coastal fog. Various lichen and moss species

were collected in Santa Cruz County, then freeze-dried and homogenized, and then analyzed for

MMHg and THg concentrations. Lichen and moss THg concentrations ranged from 31.9 to 400.4

ng g-1, with an average of 178.9±111 ng g-1. Lichen and moss MMHg concentrations ranged

from 3.86 ng g-1 to 73.3 ng g-1, with an average of 30.3±37.8 ng g-1. In a similar study the

median THg and median MMHg were found at 66.8 ng g-1 and 4.27 ng g-1 respectively. From

our preliminary data, we are optimistic that lichen and moss are good indicators of airborne

mercury concentrations. We will continue this idea by sampling along a coastal-inland transect

(fog frequency gradient) at the end of the fog season. Our study may be able to provide insight on

how MMHg and THg enter the coastal food chain through fog water deposition.

1University of California, Santa Cruz, pweiss@ucsc.edu 2University of California, Santa Cruz, wlin24@ucsc.edu 3University of California, Santa Cruz, pweiss@ucsc.edu 4University of California, Santa Cruz, kkellman@ucsc.edu 5University of California, Santa Cruz, afreeber@ucsc.edu 6University of California, Santa Cruz, brpayoun@ucsc.edu

100

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151

152

153

Proceedings Notes

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160

The National Atmospheric Deposition Program (NADP) was established in

1977 under State Agricultural Experiment Station (SAES) leadership to address the

problem of atmospheric deposition and its effects on agricultural crops, forests,

rangelands, surface waters, and other natural and cultural resources. In 1978, sites in

the NADP precipitation chemistry network first began collecting one-week, wet-only

deposition samples for analysis at the Illinois State Water Survey’s Central

Analytical Laboratory (CAL), located at the University of Illinois, Urbana-

Champaign. The network was established to provide data on amounts, temporal

trends, and geographic distributions of the atmospheric deposition of acids, nutrients,

and base cations by precipitation.

Initially, the NADP was organized as SAES North Central Regional Project

NC-141, which all four SAES regions further endorsed in 1982 as Interregional

Project IR-7. A decade later, IR-7 was reclassified as National Research Support

Project No. 3 (NRSP-3), which it remains. NRSP projects are multistate activities

that support research on topics of concern to more than one state or region of the

country. Multistate projects involve the SAES in partnership with the USDA

National Institute of Food and Agriculture and other universities, institutions, and

agencies.

In October 1981, the federally supported National Acid Precipitation

Assessment Program (NAPAP) was established to increase understanding of the

causes and effects of acidic precipitation. This program sought to establish a long-

term precipitation chemistry network of sampling sites distant from point source

influences. Because of its experience in organizing and operating a national-scale

network, the NADP agreed to coordinate operation of NAPAP’s National Trends

Network (NTN). To benefit from identical siting criteria and operating procedures

and a shared analytical laboratory, NADP and NTN merged with the designation

NADP/NTN. This merger brought substantial new federal agency participation into

the program. Many NADP/NTN sites were supported by the USGS, NAPAP’s lead

federal agency for deposition monitoring.

In October 1992, the Atmospheric Integrated Research Monitoring Network

(AIRMoN) joined the NADP. AIRMoN sites collect samples daily when

precipitation occurs. In January 1996, the NADP established the Mercury Deposition

Network (MDN), the third network in the organization. The MDN was formed to

provide data on the wet deposition of mercury to surface waters, forested

watersheds, and other receptors. In October 2009, the Atmospheric Mercury

Network (AMNet) joined the NADP as the fourth network. AMNet measures the

concentration of atmospheric mercury. In October 2010, the Ammonia Monitoring

Network (AMoN) joined the NADP, measuring atmospheric ammonia

concentrations using passive monitors.

SAES project NRSP-3 was renewed in 2014 and it continues to offer a unique

opportunity for cooperation among scientists from land-grant and other universities,

government agencies, and non-governmental organizations. It provides a framework

for leveraging the resources of nearly 100 different sponsoring agencies to address

contemporary and emerging issues of national importance.

161

NADP Program Office

Illinois State Water Survey

2204 Griffith Drive

Champaign, IL 61820-7495

NADP Home page: http://nadp.isws.illinois.edu

Phone: 217/333-7871